Organoborane-amino complex polymerization initiators and polymerizable compositions
FIELD: polymerization processes.
SUBSTANCE: invention relates to two-component composition used to initiate curing of one or more polymerizable monomers that are cured when affected by free radicals, which composition consists of organoborane-amino complex and an isocyanate capable of destroying organoborane-amino complex, wherein equivalent ratio of amine nitrogen atoms to boron atoms ranges from more than 4.0:1 to 20.0:1. In another embodiment of invention, subject of invention is two-component composition for use as sealing materials, coatings, primers for modifying polymer surfaces, and as molded resins, which composition consists of component 1: organoborane-amino complex wherein ratio of amine nitrogen atoms to boron atoms ranges from more than 4.0:1 to 20.0:1; component 2: one or more monomers, oligomers, or polymers having olefinic instauration, which are able of being subjected to free-radical polymerization; and effective amount of an isocyanate, which can initiate dissociation of complex to free borane for initiation of polymerization of one or more monomers, oligomers, or polymers having olefinic instauration, provided that complex dissociation initiator is stored separately from complex until initiation of polymerization becomes desirable. Such compositions are handling safe, i.e. they are not self-inflammable, stable at or near ambient temperature and so they do not initiate polymerization at or near ambient temperature in absence of complex dissociation initiator. Polymerized composition show good cohesion and adhesion strength. Described are polymerizable composition polymerization process, method of gluing two or more substrates using polymerizable composition; method of modifying polymer surface having low surface energy using polymerizable composition, as well as coating and laminate containing polymerizable composition.
EFFECT: enlarged resource of polymerizable compositions and expanded application areas thereof.
10 cl, 2 dwg, 4 tbl
This invention relates to compositions that contain organoborane-amine complexes, used to initiate polymerization of compounds with free radicals. In another embodiment, this invention relates to polymerizable compositions containing compounds containing particles capable of free radical polymerization, and organoborane-amine complex initiator of the invention. In yet another embodiment, the invention relates to a method of polymerization of compounds containing particles capable of free radical polymerization.
In many practical situations, in which the compounds are subjected to polymerization or where adhesives are used, it is desirable to have polymerizable compositions and adhesive compositions which can be cured on demand. Cure-on-demand means that the polymerization can be initiated when it is desirable. A significant problem cured by the needs of the tracks is the stability of the compositions. Many such compositions begin to cure at or near ambient temperature or partially otverzhdajutsja at ambient temperature, leading to increased viscosity, which causes difficulties processing and reduced the functionality of the polymerizable composition or adhesive composition.
The olefins with iscoe surface energy, such as polyethylene, polypropylene and polytetrafluoroethylene, have a number of promising characteristics in a range of applications, such as applications for toys, automobile parts and accessories. Because of the low surface energy of these polymeric materials is very difficult to find adhesive compositions that incorporate these materials. Commercially available adhesives that are used for these plastics require intensive or extensive pre-treatment of the surface before the glue connects with the surface. Such treatments include the treatment by corona discharge and flame treatment. The requirement of extensive surface treatment leads to significant limitations for designers of automotive parts, toys and accessories. So necessary are adhesive compositions which are able to connect with substrates with low surface energy and glued to the substrate with a low surface energy with other substrates without the need for extensive or expensive pre-processing.
U.S. patent 3275611 (Mottus et al.) considering the method of polymerization of olefinic compounds with a catalyst containing organoborane compound, the peroxide compound and amine. Considered that organoborane compound and the amine may be introduced into the reaction mixture is separately or as a pre-formed complex and that the complex is preferred. The presence of amine in the complex reduces samovosplameneniem of organoborane in the air. Among the amine complexing agents described pyridine, aniline, toluidine, dimethylbenzylamine and nicotine. Many of the complexes discussed in U.S. patent 3275611 (Mottus et al.), are ignite spontaneously when the ratio of amine with the boron atom. In addition, many of the amine complexes do not show significant adhesion properties when applied to substrates with low surface energy.
The number of patents granted Skoultchi (U.S. patent No. 5106928, 5143884, 5286821, 5310835 and 5376746), consider a two-component initiator system used in the acrylic adhesive compositions. The first component of a two component system includes a stable, organoborane-amine complex, and the second component includes destablizer or activator, such as an organic acid or aldehyde. Organoborane connection system has three ligand, which can be selected from C1-10-alkyl groups or phenyl groups. Describes amines include octylamine, 1,6-diaminohexane, diethylamin, dibutylamine, Diethylenetriamine, dipropylenetriamine, 1,3-Propylenediamine and 1,2-Propylenediamine. Described adhesive compositions are intended for use in structural and polyethylene adhesive applications such as magni is open, bonding metal to metal bonding of automotive glass to metal bonding glass to glass bonding components, printed circuit boards, gluing separate plastics with metal, glass, wood, etc. or for magnets of electric motors.
Zharov et al. consider the number of U.S. patents (US 5539070, US 5690780 and US 5691065) polymerizable acrylic compositions which, in particular, are used as adhesives, in which organoborane-amine complexes are used to initiate curing. Used organoborane have three ligand attached to the boron atom, which is selected from C1-10-alkyl groups and phenyl. Amin is amerosport, linear alkylamine, where the first amino group may be primary or secondary amine and the second amine is a primary amine or an aromatic substituted alkylamine. Indicated that these complexes are good for initiating polymerization of the glue that connects to substrates with low surface energy.
Pocius in several patents (US 5616796, US 5621143, US 5681910, US 5686544, US 5718977 and US 5795657) considers organoborane-amine complexes with a number of amines, such as polyoxyalkylene and polyamine, which are the product of the interaction of primary diamines and compounds having at least two groups that interact with the primary amine. US 5686544 (Pocius considers the composition, containing organoboron-polyamines complex, polyol and isocyanate complexdatatype agent. Is considered that the ratio of primary amine : boron complex is in the range from 4:1 to 1:1 and most preferably 1:1.
Many of the complexes discussed in the patents Zharov, Skoultchi and Pocius, are unstable in compositions containing olefinic unsaturation, at or near ambient temperatures, and thus, the complexes decompose and induce polymerization at or near ambient temperature over time. This instability at or near the ambient temperature can give a polymerization previously desired and can give compositions which are unsuitable for the desired use. In addition, the compositions are two-component compositions, in which one component is a polymeric component and the other component is a hardener. One component (hardener) contains organoborane complex, and the other contains complexdatatype agent. In most cases, the volumetric ratio of the two components varies significantly, i.e. is more than 4:1, often more than 10:1. The problem is that most commercial equipment for dispensing two-component compositions, uses a ratio of 4:1 or is the Eney. In order to be able to handle these compositions in such equipment, add resin or directionspanel ingredients with one or the other end for receiving a suitable volume ratio. The problem is that if the resin is added to the component containing the complex, the mixture is unstable and may begin to cure at ambient temperatures, and the composition becomes unsuitable. If excess inert materials injected into the hardener component, inert ingredient may act as a plasticizer or create a weak continuous phase and adversely affect the properties of the cured composition.
After polymerization of many famous compositions show excellent stability, durability and adhesion at or near ambient temperatures, but at elevated temperatures lose their strength and adhesion at significantly elevated temperatures. This limits the conditions that can be used for the substrate, glued using these adhesives.
Therefore there is a need for systems initiator for free radical polymerization, which are safe for handling, nesamovsasyvayuschimi, which can be used for curing on the needs of polymeric systems or can be used in the adhesive with the systems, which otverzhdajutsja on demand. In addition, the required adhesive systems, which are able to glue the substrate with a low surface energy, and the initiator system that facilitate such bonding. In addition to these requirements, the complexes must be heat-resistant, i.e. should not dissociate at or near ambient temperatures and therefore to initiate the polymerization prematurely. There is therefore need for polymer compositions and adhesive systems, which are heat-resistant at or near ambient temperatures and which polymerize when the user really wants. In addition, the required composition, which can be used in existing commercial equipment in the mixing ratios of 4:1 or less. Desirable are songs that have stability, durability and adhesion at elevated temperatures.
The subject of the invention is a two-component composition used to initiate curing of one or more polymerizable monomers, which otverzhdajutsja when exposed to free radicals, consisting of one component of organoborane-amine complex and the second isocyanate component that is capable of destroying organoborane complex, in which the ratio of nitrogen atoms of the amine to boron atoms is over ,0:1,0.
In another embodiment, the subject invention is a two-component polymerizable composition containing
component 1 - a) organoborane-amine complex, in which the ratio of nitrogen atoms of the amine to boron atoms is greater than 4.0:1, and
component 2 - b) one or more monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization free radical polymerization. In a preferred embodiment, the second component (component 2) additionally contains an effective amount of isocyanate, which causes dissociation of the complex component 1, the release of the borane to initiate polymerization of one or more monomers, oligomers or polymers having olefinic unsaturation. In this embodiment complexdatatype agent and the complex are contained in different components to prevent premature reaction.
The subject of the invention is also a method of polymerization comprising the contacting of the components of the polymerizable composition under such conditions that one or more of monomers, oligomers or polymers undergo polymerization. In one embodiment, the contacting occurs at or near ambient temperature. In another embodiment, the method further comprises the stage of heating the polymerized composition to improve the temperature in such conditions, that amine and isocyanate can interact. This can improve the resistance of the cured composition.
In another embodiment, the subject invention is a method of bonding two or more substrates together which comprises contacting the polymerizable components of the composition together in such conditions that initiate polymerization; contacting the polymerizable composition with two or more substrates; placing two or more substrates so that the polymerizable composition is placed between two or more substrates, and carrying out polymerization of the polymerizable composition and bonding two or more substrates together.
In another embodiment, the subject invention is a method of coating composition to the substrate, which comprises contacting a composition containing
and organoborane-amine complex, in which the ratio of nitrogen atoms of the amine to boron atoms is greater than 4.0:1, and
b) one or more monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization free radical polymerization with one or more surfaces of the substrate,
and heating the coating to the initiation of the curing of the coating.
In another embodiment, the subject invention is a method of coating substrates, in which the composition is ocrite contains
and organoborane-amine complex, in which the ratio of nitrogen atoms of the amine to boron atoms is greater than 4.0:1;
b) one or more monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization free radical polymerization, and
(C) the agent of the destruction complex.
In another embodiment, the subject invention is a laminate comprising two substrates having located between the substrate and connected with each substrate composition, containing
and organoborane-amine complex, in which the ratio of nitrogen atoms of the amine to boron atoms is greater than 4.0:1, and
b) one or more monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization free radical polymerization.
The composition in such a laminate may further comprise the agent of the destruction complex.
In another embodiment, the subject invention is a two-component polymerizable composition containing
component 1 - a) organoborane-amine complex;
component 2 - b) one or more monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization free radical polymerization;
(C) an effective amount of a compound that causes dissociation of the complex for MF is t which is the liberation of the borane to initiate polymerization of one or more monomers, oligomers or polymers having olefinic unsaturation, where the connection, which causes dissociation of the complex was kept separately from the complex, until initiation of polymerization is not desirable, and
d) material, which regulates the heat of the polymerization reaction, so that supported the adhesion to the substrate, and the material can be located either component 1 or component 2, or in both components.
The complexes of the invention are safe to handle, i.e. not ignite spontaneously, are stable at or near ambient temperature and therefore do not initiate polymerization at or near the ambient temperature in the absence of initiator, which causes dissociation of the complex. The polymer compositions of the invention are stable at or near ambient temperature and can be cured on demand when contacting the complex with compounds that cause dissociation of the complex, or, alternatively, by heating the polymer compositions above the temperature of thermal dissociation of the complex. In addition, polymerizable compositions of the invention can form a good connection with substrates with low surface energy without the need for primers or surface treatment. These polymerizable component is icii can be used as adhesives, coatings and can be used for laminating the substrates together. Systems and polymerizable compositions of the invention can be prepared according to the recipe, to be able to hand in the commercial equipment at volume ratios of the two components of the 4:1 or less. The cured compositions exhibit excellent cohesive and adhesive strength at elevated temperatures and, thus, exhibit excellent stability at high temperatures.
Figure 1 presents the shear strength of lap joints adhesives as a function of atomic relations amine to the Bor.
Figure 2 shows the rate of curing of adhesives with different atomic relations of the amine nitrogen to the forest.
Detailed description of the invention
Organoboranes used in the complex is trialkylborane or alkylcyclobutanones. Preferably such borane corresponds to the formula 1
where is boron, and R2is separately in each case With1-10-alkyl, C3-10-cycloalkyl or two or more R2can be combined with the formation of a cycloaliphatic ring. Preferably R2is1-4-alkyl, even more preferably2-4-alkyl and most preferably3-4-alkyl. Among organoboron preference is sustained fashion are triethylborane, triisopropylsilane and tri-n-butylborane.
To obtain heat polymerizable compositions require heat-resistant complexes that do not dissociate at or near ambient temperature. The main principle of such systems is the choice of amine. The suitability of the use of this amine in organoborane-amine complex can be calculated from the energy difference between the complex of the Lewis acid-Lewis base and the sum of energies of individual acid Lewis (organoboron) and a separate base Lewis (Amin), known as the binding energy. The higher (more negative) binding energy, the more stable the complex.
The binding energy = (Energy complex(the energy of the Lewis acid+Energy base Lewis))
Such energy can be calculated using theoretical initially methods such as a method of self-consistent field Hartree-Fock and basis set 3-21G. These computational methods are commercially available, using commercial computer programs, such as programs SPARTAN and GAUSSIAN 98 c Silicon Graphics workstation. Amines having a bond energy Amin - organoboron 10 kcal/mol or more, are preferred amines having a bond energy Amin - organoboron 15 kcal/mol or more, are more preferred and even more preferred is entrusted are amines with energy of 20 kcal/mol or more. In a variant, where the polymerization of the compositions of the invention is initiated when using complexdatatype agent, the binding energy of Amin with organoboranes is preferably 50 kcal/mol or less and most preferably 30 kcal/mol or less. In a variant, where the polymerization of the compositions of the invention is initiated by the use of heat energy due amine is preferably 100 kcal/mol or less, more preferably 80 kcal/mol or less and most preferably 50 kcal/mol or less.
Amines used for complexation with organoboranes connection can be any amine or mixture of amines, which form a complex with organoboranes and which may be released from the complex upon exposure complexdatatype agent. Preferred amines include primary or secondary amines or polyamine containing primary or secondary amino group or ammonia, as discussed in US 5539070 (Zharov), column 5, lines 41-53, US 5106928 (Skoultchi), column 2, line 29-58, and in US 5686544 (Pocius), column 7, line 29 to column 10; ethanolamine, secondary dialkylamines or polyoxyalkylene, and the reaction products of end amino groups of the diamines and compounds having two or more groups that interact with amines as described in US 5883208 (Deviny), column 7, line 30 to column 8, line 56. What concerning the Xia reaction products, described in the latter patent, the preferred primary diamines include primary alkylamine, primary ariginine, primary ascaridiasis and polyoxyalkylene; compounds that interact with the amines include compounds that contain two or more groups of carboxylic acids, esters of carboxylic acids, halides of carboxylic acids, aldehydes, epoxides, alcohols and acrylate groups. Preferred amines include n-octylamine, 1,6-diaminohexane (1,6-hexanediamine), diethylamin, dibutylamine, Diethylenetriamine, dipropylenetriamine, 1,3-Propylenediamine (1,3-propandiamine), 1,2-Propylenediamine, 1,2-amandemen, 1,5-pentanediamine, 1,12-dodecandioic, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, Triethylenetetramine, Diethylenetriamine. Preferred polyoxyalkylene include polyethylenoxide, polypropyleneimine, triethylenediamine, polytetramethylene and poliatilenaksida-polypropyleneoxide.
In one preferred embodiment, the amine contains a compound having a primary amine and one or more groups that accepts a hydrogen bond, where there are at least two carbon atoms, preferably at least three, between the primary amine and groups that accept a hydrogen bond. Preferably alkalinity residue is located between the primary is the first amine and the group, accepting a hydrogen bond. The group accepts a hydrogen bond, means a functional group which either by inter-or intramolecular interaction of the amine with hydrogen, forming a complex with borane, increases the electron density of the nitrogen of the amino group, forming a complex with borane. The preferred group that accepts a hydrogen bond include primary amines, secondary amines, tertiary amines, ethers, halogen, polyethers, simple thioethers and polyamine. In a preferred embodiment, the amine corresponds to the formula 2
in which R1in each case represents hydrogen, C1-10-alkyl, C3-10-cycloalkyl or two or more R1may form a cyclic ring structure, which may have one or more cyclic rings;
X represents an acceptor of hydrogen;
a represents an integer from 1 to 10 and
b in each case is an integer from 0 to 1, and the sum of a and b is equal to from 2 to 10.
Preferably, R1represents hydrogen, methyl, or two or more R1connected with the formation of 5 - or 6-tier circular ring. In a preferred embodiment, X represents an acceptor of hydrogen, provided that when the acceptor of hydrogen is Amin, he is the tertiary sludge is a secondary amine. More preferably X is separately in each case,- N(R8)e, -OR10, -SR10or halogen. R8separately in each case is1-10-alkyl, C3-10-cycloalkyl, -(C(R1)2)d-W, or two R8can be connected with the formation of patterns having one or more cyclic rings. R10separately in each case is1-10-alkyl, C3-10-cycloalkyl or -(C(R1)2)d-W. E. separately in each case is 0, 1 or 2 and most preferably e is 2. More preferably X is-N(R8)2or10. Preferably R8and R10are1-4-alkyl or -(C(R1)2)d-W, more preferably1-4-alkyl and most preferably methyl. W separately in each case represents hydrogen or C1-10-alkyl, or X, and, more preferably hydrogen or C1-4-alkyl. Preferably and is 1 or more and more preferably 2 or more. Preferably and is 6 or less, and most preferably 4 or less. Preferably b is 1. Preferably the sum of a and b is an integer of 2 or more and most preferably 3 or more. Preferably the sum of a and b is equal to 6 or less and more preferably 4 or less. Preferably d is separately in each case is a the th number from 1 to 4, more preferably 2-4, and most preferably 2-3. Among the amines corresponding to formula 2, are preferred dimethylaminopropylamine, methoxypropylamine, diethylaminoethylamine, diethylaminoethylamine, methoxybutyl, methoxyethylamine, ethoxypropylamine, propoxyphene, simple polyalkylene with terminal amine groups, such as a simple Tris-(polypropyleneglycol) ether of trimethylolpropane with terminal amine groups and aminopropylmorpholine.
In one embodiment, the preferred amine complex corresponds to the formula 3
in which R1, R2, X, a and b are as previously defined.
In another embodiment, the amine is aliphatic heterocycle having at least one nitrogen heterocycle. The heterocyclic compound may also contain one or more nitrogen atoms, oxygen, sulfur or double bonds. In addition, the heterocycle can contain multiple rings, where at least one of the rings has a nitrogen in the ring. Preferably aliphatic heterocyclic amine corresponds to the formula 4
in which R3in each case represents hydrogen, C1-10-alkyl With3-10-cycloalkyl or forms a double bond with an adjacent atom. R4'separately to the each case represents hydrogen, With1-10-alkyl or forms a cyclic ring with R3Z or Deputy on Z. Z in each case represents sulfur, oxygen or-NR4. R4in each case represents hydrogen, C1-10-alkyl or C6-10-aryl, or C7-10-alkaryl. x is separately in each case represents an integer from 1 to 10, provided that the sum of all cases, x must be from 2 to 10. y is separately in each case equal to 0 or 1. Two or more R3, R4and R4'can connect to the formation of cyclic rings, producing the cyclical connection. Preferably R3in each case represents hydrogen, methyl or forms a double bond with an adjacent atom. Preferably Z represents NR4. Preferably R4represents hydrogen or C1-4-alkyl and more preferably hydrogen or methyl. Preferably R4'represents hydrogen or C1-4-alkyl, more preferably hydrogen or methyl and most preferably hydrogen. Preferably x is equal to from 1 to 5, and the sum of all cases, x is equal to 3-5. Preferred compounds corresponding to formula 4 include morpholine, piperidine, pyrrolidine, piperazine, 1,3 .3m-trimethyl-6-azabicyclo[3,2,1]octane, thiazolidine, homopiperazin, aziridine, 1-amino-4-methylpiperazine, 3-pyrrolin and aminopropylmorpholine. The complex is, containing aliphatic heterocyclic amines, preferably correspond to the formula 5
in which R2, R3, R4', Z, x, and y are as previously defined.
In yet another embodiment, an amine, which forms a complex with organoboranes is amidin. Can be used in any connection with the structure of amidine where amidin has enough power connection, as defined previously, with organoboranes. Preferred compounds of amidine correspond to the formula 6
in which R5in each case represents hydrogen, C1-10-alkyl or C3-10-cycloalkyl. R6in each case represents hydrogen, C1-10-alkyl, C3-10-cycloalkyl or N(R5)2. Two or more R5, R6and R7can be connected in any combination with the formation of the ring structure, which may have one or more rings. Preferably R5in each case represents hydrogen, C1-4-alkyl or C5-6-cycloalkyl. Preferably R6in each case represents hydrogen, C1-4-alkyl or C5-6-cycloalkyl or N(R5)2. More preferably R6separately in each case is1-4-alkyl or C5-6-cycloalkyl is N? (R 5)2. Preferably R7in each case represents hydrogen, C1-10-alkyl, C3-10-cycloalkyl or part of a ring structure. Most preferably, R7represents hydrogen, methyl or part of a cyclic ring. In one embodiment, where two or more R5, R6and R7connected with the formation of the ring structure, the ring structure is preferably a single or double ring structure. Among the preferred amidines are 1,1,3,3-tetramethylguanidine, 1,8-diazabicyclo[5,4]undec-7-ene, tetrahydropyrimidin and 2-methyl-2-imidazolin.
Organoboron-amidinov complexes preferably correspond to the formula 7
in which R2, R5, R6and R7are as previously defined.
In another embodiment, an amine, which forms a complex with organoboranes is the conjugate Imin. Can be used in any connection with the structure of the conjugated imine, where Imin has enough power connection, as defined previously, with organoboranes. Paired Eminem can be Imin straight or branched chain or cyclic Imin. Preferred imine compounds correspond to the formula 8
in which Y is independently in each case is in the location, N(R4)2, OR4C(O)OR4, halogen, alkylenes group which forms a cyclic ring with R7or R9. R9independently in each case is hydrogen, Y1-10-alkyl, C3-10-cycloalkyl, (C(R9)2-(CR9=CR9)cY or two or more R9can be connected with the formation of a ring structure, provided that electronmobility group in Y is conjugate relative to the double bond of the imine nitrogen and C represents an integer from 1 to 10. Preferably R9represents hydrogen or methyl.
Y preferably represents-N(R4)2, SR4, OR4or alkilinity group which forms a cyclic ring with R9. Y preferably represents-N(R4)2or alkilinity group which forms a cyclic ring with R9. Preferably represents an integer from 1 to 5 and most preferably 1. Among the preferred conjugate Iminov used in this invention are 4-dimethylaminopyridine, 2,3-bis-(dimethylamino)cyclopropenone, 3-(dimethylamino)acroleine and 3-(dimethylamino)methacrolein.
Among the preferred cyclic Iminov are cyclic imine corresponding to the following structures:
Complexes with sprage the governmental Minami preferably correspond to the formula 9
(R2-)3-B NR7= CR9- (CR9= CR9)cY Formula 9
in which R2, R7, R9, c and Y are as previously defined.
In another embodiment, the amine may be alicyclic compound having communication with the Deputy alicyclic ring containing amine residue. Aminecontaining alicyclic compound may have a second Deputy, which contains one or more nitrogen atoms, oxygen, sulfur or a double bond. Alicyclic ring may contain one or two double bonds. Alicyclic compound may have a single or multiring structure. Preferably the amine on the first Deputy is primary or secondary. Preferably alicyclic ring is 5 - or 6-tier ring. Preferably the functional groups on the second Deputy are amines, ethers, simple thioesters or halides. In a preferred embodiment, the alicyclic compound with one or more aminobenzamide substituents correspond to the formula 10
in which R3, X, b and x are as previously defined. In eminememinem alicyclic compounds include isophorondiamine and isomers of bis-(aminoethyl)cyclohexane.
The complexes using Aminzade the military alicyclic compounds correspond to the formula 11
in which R2, R3, X, b and x are as previously defined.
The equivalent ratio of amine compounds (compounds) and boranova compounds in the complex is relatively important. The excess amine is preferred to facilitate the negotiation of the amount of resin component and hardener component in the polymerizable compositions described herein. Additional increase in amine content additionally stabilizes organoborane-amine complex. In addition, amine interacts with the agent of the destruction complex with obtaining thermally stable urea, politician or polyurea/urethane. Preferably the equivalent ratio of amine compounds and organoboranes connection is 4.0:1.0 or more. More preferably, the equivalent ratio of amine compounds and organoboranes connection is more than 4.0:1,0, even more preferably of 5.0:1.0 or greater and most preferably from 6.0:1.0 or more. The upper limit on the number of amine based on the amount of heat emitted during the interaction of the amine and isocyanate agent of the destruction complex, and the number present agent of the destruction complex, as discussed below. More preferably, the equivalent ratio is s amine compounds and organoboranes connection is to 20.0:1.0 or less, and most preferably at 16.0:1.0 or less.
Polymerizable compounds that can be used for the polymerization of compounds of the invention include any monomers, oligomers, polymers or mixtures thereof, which contain olefinic unsaturation, which may polymerization free radical polymerization. Such compounds are well known to specialists in this field. In U.S. patent No. 3275611, Mottus, presents a description of these compounds in column 2, line 46, - column 4, line 16. Among preferred classes of compounds having olefinic unsaturation, are monomers, oligomers, polymers and mixtures thereof, derivatives of acrylates and methacrylates; hydrocarbons with olefinic-unsaturated, for example ethylene, propylene, butylene, isobutylene, 1-octene, 1-dodecene, 1-heptadecene, 1 achozen; vinyl compounds such as styrene, vinylpyridine, 5-methyl-2-vinylpyridine, vinylnaphthalene, alpha methylsterol; vinyl and vinylidenechloride; Acrylonitrile and Methacrylonitrile; vinyl acetate and finalproject; vinyloxyethyl; vinyltrimethylsilane; vinylketones; vieillard; vinylchloride; ministart; methyl vinyl ketone are; minimizebutton ether; unilateraly ether; compounds that have a lot of ethylene linkages, such as compounds having conjugated double bonds such as butadiene, 2-chlorobutadiene and isoprene. Examples of preferred acrylate is in and methacrylates discussed in U.S. patent No. 5286821 (Skoultchi), column 3, line 50 to column 6, line 12, and in U.S. patent No. 5681910 (Pocius), column 9, line 28 to column 12, line 25. The preferred olefinic compounds include methyl acrylate, methyl methacrylate, butylmethacrylate, tert-butylmethacrylate, 2-hexyl acrylate, 2-ethylhexylacrylate, acrylate, isobornylacrylat, isobutylacetate, hydroxyethylmethacrylate, glycidylmethacrylate, tetrahydrofurfurylamine, acrylamide, n-methylacrylamide and other similar galatsaray monomers. Also used class of polyurethane prepolymers with acrylate end groups, commercially available from multiple sources and received by the interaction of reactive towards isocyanate acrylate monomer, oligomer or polymer, such as hydroxyacrylates, with a prepolymer with isocyanate functionality.
In a variant, where the composition is used as an adhesive, preferably used are acrylate - and/or methacrylaldehyde connection. The most preferred acrylate and methacrylate compounds include methyl methacrylate, butylmethacrylate, 2-ethylhexylacrylate, isobornylacrylat, tetrahydrofurfurylamine and cyclohexanedimethanol.
Preferably the cured composition of the invention can form a polymer that has a high termostatic the industry. High resistance means that the polymer is not significantly softened or not subject to degradation at elevated temperatures. Preferably, the polymer is capable of withstanding temperatures in excess of 10°C expected maximum application temperature. Preferably this temperature is 60°C or higher and more preferably 90°C or higher. The preferred monomers which give polymers with high thermal stability, are methyl methacrylate (MMA) and isobornylacrylat. Preferred-resistant polymers are spma (syndiotactic polymethyl-methacrylate), PMMA (polymethylmethacrylate), polyisobutenylsuccinic, polyacrylamide and cross-linked (meth)acrylic polymers.
Compositions of the invention additionally contain an effective amount isocyanatobenzene connection (the agent of the destruction complex, which interacts with formed a complex with the amine, so that frees organoboron and initiates polymerization. Reactive towards amine compound releases organoboron when interacting with an amine, removing as a result of organoboron from chemical attach to the amine. Desirable agents of destruction of the complex are such isocyanates, which can easily form reaction products with amines at or below is more preferable at room temperature, i.e. 20-22°C, so that it was possible to obtain a composition which is easily used and cured in ambient conditions. Preferably the amount present isocyanatobenzene connection is sufficient to cause decomposition of organoborane-amine complex is present in the composition. Preferably there is enough present isocyanatobenzene connection to communicate with everyone with the amine. Excess amine can plastifitsirovanie formed polymer and, thus, jeopardize the properties of the formed polymer. Preferably there is an excess of isocyanate compared to free the total number of active hydrogens (usually primary and secondary amine and hydroxy-group in organoborane-amine complex. Preferably the ratio of isocyanate equivalents to amine equivalents is 1.0:1.0 or more, more preferably of 1.1:1.0 or more and most preferably of 1.25:1 or more, as used here, it refers to any free amine and amine present, formed a complex. Isocyanatobenzene compounds interact with the amine present in the composition, with the formation of urea, polyurea or polyurethane/urea phase. When used in excess isocyanatobenzene connection, get the product there is little or not there is a free amine. With the exception of the presence of free amine plasticizing effect of amine is prevented. In addition, the presence of urea or polyurea improves the heat resistance of the obtained product. Preferably urea or polyurea present in the resulting polymerized product is 5 wt.% or more, more preferably 10 wt.% or more, and most preferably 15 wt.% or more. Preferably the amount of polyurea present in the resulting polymerized product is 50 wt.% or less, more preferably 45 wt.% or less and most preferably 40 wt.% or less. The percentage of urea means wt.% phase urea/urethane in the final product. This can be usually determined by adding the mass of the isocyanate and amine (and any other present compounds reactive towards isocyanate) and dividing this amount by the total weight of the ingredients.
In one embodiment, the polymer or adhesive formulation of the invention may additionally contain one or more compounds that have more than one, preferably two or more residues that interact with isocyanates. Usually, in addition to amines, residues, which contain active hydrogen atoms interact with isocyanate groups, such residues include hydroxyl, CT is axiety and Tilney residues. After amines are more preferred residues with active hydrogen atoms are hydroxyl residues. The preferred hydroxyl-containing compounds are polyols and aminogly. Can be used any polyol that is used to communicate with the isocyanates. Preferably primary and secondary amines are the only compounds which are present to interact with isocyanatobenzene connections. Preferably isocyanatomethyl connection is any isocyanate compound, which decomposes organoborane-amine complex. Preferably the isocyanate is a polyisocyanate having nominally 2 or more isocyanate residues on the connection. Used isocyanate compounds are discussed in US 5872197 (Deviny), column 4, line 57 to column 5, line 65. Among the more preferred isocyanatomethyl compounds are polymeric options etilendiamindisuktsinatov, isophorondiisocyanate, hexamethylenediisocyanate, colorvision, isomers or bis-isocyanatomethyl and tetramethyldisilane.
Preferably the amount of polymerizable compounds in the polymerizable compositions or adhesives is 20 wt.% or more relative to the weight of the entire composition, more preferably 30 wt.% or more and Nai is more preferably 40 wt.% or more. Preferably the amount of polymerizable compounds is 95 wt.% or less, more preferably 90 wt.% or less, and most preferably 85 wt.% or less. The amount of the complex used in the composition can be any amount sufficient to initiate polymerization, as soon as the complex dissociates. At higher concentrations of organoborane the polymerization rate is usually higher. Preferably the amount present organoborane complex is sufficient to provide a quantity of boron 0.02 wt.% or more relative to the weight of the entire composition, and more preferably of 0.05 wt.% or more. Preferably the amount present organoborane complex is sufficient to provide a quantity of boron to 1 wt.% or less relative to the weight of the entire composition, preferably 0.7 wt.% or less, and most preferably 0.4 wt.% or less.
Preferably the amount present isocyanate is 80 equiv.% or more relative to the equivalents of amine present, as part of the complex and free, more preferably 100 EQ.% or more, and most preferably 110 EQ.% or more.
Organoborane-amine complex can be easily obtained using known techniques. Usually Amin kombineret organoboranes in an inert atmosphere with stirring. Often observed ectotherm, and therefore it is recommended that the cooling of the mixture. If the ingredients have a high vapor pressure, it is desirable to maintain the reaction temperature below 70-80°C. as soon As the materials mix well, allow to cool to room temperature. The solvent is then removed. Special storage conditions are not required, although it is preferable that the complex was kept in the closed lid of the vessel in an inert atmosphere in a cool dark place. Mostly complexes of the invention can be obtained in the absence of organic solvents, which then must be removed, although they can be obtained in the solvent, if so required. Solvents used in obtaining complexes must be such solvents, which do not coordinate amine, preferably solvents are, for example, tetrahydrofuran or diethyl ether, or a low molecular weight alkanes, such as hexane or heptane.
The complexes used in the invention are vozduhotehnika. Under "vozduhotehnika" means that when the complexes are stored in the closed lid of the vessel at room temperature (20-22° (C) in the different environments (i.e., not in a vacuum and not in an inert atmosphere), the complexes remain to be used as polymerization initiators for at least two weeks,although the complexes can easily be stored under these conditions for many months.
Under "vozduhotehnika" it is also understood that the complexes are not ignite spontaneously. (When a few drops of the complex is placed on a paper napkin in ambient conditions, paper napkin not flammable, not chars and not Smoking). Vozduhoochistki complex improves when the complex is a crystalline material. However, the complexes of the invention are vozduhotehnika for at least six months, even when they are liquids. Liquid systems are easier to handle and mix than crystalline complexes.
Polymerizable compositions of the invention are two-component compositions. In one embodiment, the compositions are two-component compositions, in which one component contains the complexes of the invention and the other component contains complexdatatype agent (the initiator). Polymerization is initiated by contacting the two components of the composition. Polymerization can be initiated at or even below ambient temperatures. To the polymerizable composition can be summed up heat to accelerate the initiation or polymerization and to facilitate interaction present isocyanate compounds with compounds containing active hydrogen. The main reason for the use of two-component composition which is the content of the individual components of the composition, which can be unstable in the presence of each other.
In the variant where the use of heat to effect the curing of the composition, the composition is exposed to a heat source which heats the composition at a temperature at or above the temperature at which the complex used in the composition decomposes with release of organoborane, which then initiates free radical polymerization. Typically, the composition is heated to a temperature which is less than the temperature at which the monomer undergoes spontaneous polymerization. The temperature at which the complex undergoes dissociation, is associated with the binding energy of the complex. At higher energies due to the complex requires a higher temperature to initiate polymerization.
When the binding energy of the complex is high, the polymerization can be initiated thermally. The temperature at which the composition is heated to initiate polymerization is dictated by the binding energy of the complex. Typically, the temperature used to initiate polymerization upon decomposition of the complex is 30°C or more and preferably 50°C or more. Preferably the temperature at which is initiated thermally initiated polymerization, 120°C or less and more preferably 100°C and and less. You can use any heat source which heats the composition at the desired temperature, provided that the heat source does not impact negatively on the components of the composition or function. This way, the composition can be contacted with the substrate either before or after the composition affects the heat. If the composition is heated before contact with the substrate, the composition should be in contact with the substrate before the composition cures at the moment at which the composition is no longer able to adhesivity to substrates. In thermally initiated reactions may be necessary to adjust the oxygen content, so that there is adequate oxygen to create favorable conditions for the formation of radicals, but not so much to inhibit polymerization.
If heat is used (in addition to the initiator) to improve the curing of the applied heat can be fed immediately or with a delay (i.e. some time after utverzdenija at room temperature). If you use heat with delay or heating after curing, the cured composition can be cured at temperatures much higher or slightly higher than the expected maximum application temperature. Preferably any heat with delay is applied after mastigomycotina strength utverzhdenii composition at room temperature. If the heat is supplied immediately to the cured composition to accelerate curing, then this heating is preferably less than or approximately equal to the temperature of dissociation of organoborane-amine complex.
Two-component compositions or adhesive compositions of the invention are uniquely suited for use with conventional commercially available transfer equipment for two-component adhesives. As soon as the two components are mixed, the composition should be used quickly, as the viability (setting time) can be short depending on the monomer mixture, the amount of the complex and the temperature at which shall be used for bonding. The adhesive composition is applied on one or both substrates and then the substrates are combined together preferably compressed to squeeze the excess composition from the adhesive joint. In General, the bonding must be done quickly after application of the composition, preferably within 10 minutes of the Usual thickness of the adhesive seam is between 0.005 inch (0.13 mm) to 0.03 inch (0.76 mm). The adhesive joint may be thicker, if you want to fill the gap, as the composition of the invention can act both as an adhesive and as a gap filler. Method of bonding can be easily carried out at room temperature the re, and to improve the degree of bonding, it is desirable to maintain the temperature below 40°C, preferably below 30°C and most preferably below 25°C.
Adhesive bonding otverzhdajutsja to obtain sufficient cohesive strength, allowing the appeal with the bonded components for 0.5-3 hours Full strength will be achieved within 24 h in ambient conditions. If necessary, can be used polyommatinae heating. Once initiated polymerization of olefinic composition, the composition of the invention can be maintained in conditions causing additional interaction MDI with a compound reactive toward isocyanate. Preferably this interaction is initiated by exposure of the composition at a temperature at which the polyisocyanate is reacted with a compound reactive toward isocyanate. In another embodiment, the composition may contain a catalyst for the reaction of isocyanate with a compound reactive toward isocyanate. Such catalysts are well known in the art. Temperature paleocurrent are preferably 25°C or more, more preferably 30°C and most preferably 35°C or more.
The composition can optionally contain a variety of optional additives. One is th especially used additive is a thickener, such as environments with high molecular weight (10000-1000000) polymethyl methacrylate, which can be entered in the amount of 10-60 wt.% in relation to the total weight of the composition. Thickeners can be used to increase the viscosity of the composition to facilitate application of the composition.
Another particularly used additive is an elastomeric material. Materials can improve the viscosity at the destruction of compositions made with them, which may be favorable for bonding, for example, a rigid high strength material such as a metal substrate, which is mechanically not absorb energy as easily as other materials, such as flexible polymeric substrate. Such additives can be incorporated in the amount of 5-35 wt.% in relation to the total weight of the composition. Used elastomeric modifiers include chlorinated or chlorosulphurized polyethylene, such as Hypalon 30 (commercially available from the company E.I.Dupont de Nemours & Co., Wilmington, Delaware), and block copolymers of styrene and conjugated dienes (commercially available from the company Dexco Polymers under the trademark VECTOR and from the firm Firestone under the trademark STEREON). Also used and even more preferred are some of the grafted copolymer resin, such as particles that contain rubber or koutsokoumnis core or meshes, which the material is s relatively hard shells, these materials are often referred to as polymers of type "core-shell". Most preferred are graft copolymers Acrylonitrile-butadiene-styrene, available from the company Rohm and Haas. In addition to improving the viscosity at the destruction of the compositions, the polymers of type "core-shell" can also give improved nanoselect and the flow properties of the uncured composition. These improved properties can be shown a reduced tendency of the composition to the abandonment of unwanted tissue in the hand applicator syringe type or influx, or slipping after application to a vertical surface. Use of more than 20 wt.% the additive polymer of the type "core-shell" is desirable to achieve improved resistance to the influx is slipping. Usually the number used to improve the impact strength of the polymer is such an amount which gives the desired impact strength of the resulting polymer or glue.
In a preferred embodiment, compositions of the invention contain teploreguliruth material. Can be used any material which is heat dissipation in the polymerization process. The examples used teploreguliruth materials include volatile liquids that evaporate during the reaction as a result of absorption of heat released in the reaction, the materials the e act as heat sinks in the absorption of released heat, and materials that interact by endothermic reaction under the reaction conditions. The materials used as heat sinks, are materials with high heat capacities. Examples of materials with high heat capacities include ceramic particles, glass beads, fluoropolymer powders and hollow spheres. Used liquid materials include chlorinated alkanes, dialkyl ethers, alkanes, methylene chloride and low-boiling petroleum ethers. More preferred solvents include methylene chloride, diethyl ether, pentane and hexane. The number teploreguliruth of a given material depends on the reaction temperature and the heat capacity teploreguliruth material. Specialist in the art can easily determine the required number teploreguliruth material. The heat of reaction may also be affected by slow mixing with the provision in the slower heat dissipation. Preferably, the average temperature of the adhesive in the course of his working time is regulated with job 70°C or less, preferably 60°C or less and most preferably 50°C or less. Teploreguliruth material can be placed either in the resin component of the formulation or component of the hardener. The choice teploreguliruth material and the number is and teploreguliruth material due to the amount of heat want to dispel in the polymerization process. If the heat released in the reaction is too high for too long period of time, it can adversely affect the adhesion of the cured composition to the substrate. It is desirable to limit the amount of heat induced decomposition of organoborane-amine complex. If the complex decomposes too quickly, it negatively affects adhesion. In one embodiment, using teploreguliruth materials, the ratio of nitrogen atoms to boron atoms may be any feasible relationship. In addition, when used teploreguliruth materials may be used any known organoborane-amine complexes and agents dissociation.
Another common additive is a crosslinking agent. Cross-linking agents can be used to improve resistance to solvents, adhesive bonding or polymer composition, although some compositions of the invention have good resistance to solvents, even in the absence of input from the outside cross-linking agents. A crosslinking agent may increase the temperature and solvent resistance of the cured polymer or adhesive. Usually used in amounts of 0.2 to 10 wt.% in relation to the total weight of the composition of the used crosslinking agent which includes a variety of diacrylate, mentioned above as a possible modifier acrylic monomers and compounds with acrylate and isocyanate functionality, as well as other materials. Specific examples of suitable crosslinking agents include etilenglikolevykh, etilenglikolevye, triethyleneglycoldinitrate, diethylene glycol-bis-methacryloxyethyl, polietilenglikolmonostearat, tetraethylethylenediamine, deglycerinated, detranscendentalized, pentaerythrityl, trimethylolpropane-Tris-(2-methyl-1-aziridination, trimethylolpropane, polyurethanebased the prepolymers with terminal acrylate groups, polyetherdiamine and dimethacrylate.
Optional can be enabled peroxide (typically about 2 wt.% or less relative to the total weight of the composition), for example, to regulate the speed at which the polymerized composition, or to complete the polymerization.
Small amounts of inhibitors, such as phenols employed (i.e. 2,6-di-tert-butyl-4-METHYLPHENOL), can be used, for example, to prevent or reduce degradation of olefinic monomers during storage. The inhibitors can be entered in the quantity of material does not reduce the rate of polymerization or the ultimate properties of the adhesive or other compositions derived from them, is commonly 10-10000 hours/million in relation to the weight of polymerizable monomers.
The composition may also contain a known catalyst for the reaction of compounds reactive towards isocyanate with isocyanatomethyl connection. Such catalysts are well known in the art and discussed in US 5623044 (Chaio), column 6, line 1 - line 12.
The composition of the invention may contain a reactive or research considers non reactive diluent to negotiate volume two components of the composition so as to obtain a commercially acceptable ratio of the two components. Preferably the diluent is a reactive diluent. Preferred reactive diluents are compounds reactive towards isocyanate, because they interact with the polyisocyanate with the formation of the polyurea and/or polyurethane phase. Representatives of this class of additives are having a low equivalent weight alcohols, amines, aminogly, polyamine, polyols or mixtures thereof. These reactive additives interact with the isocyanate (complexdatatype agent), and, thus, the number of isocyanate should be increased to offset these additives. Phase polyurea/polyurethane can improve the properties of the final product. Typically, this phase can increase the glass transition temperature of education the aqueous polymeric adhesive. The properties of the final utverzhdenii composition may be regulated by the choice of MDI and compounds reactive towards isocyanate.
Other possible additives include research considers non reactive dyes, fillers, solvents, etc. Solvents should be selected to have a boiling point below the temperature of thermal decomposition of organoborane-amine complex. The use of excess research considers non reactive diluent may adversely affect some properties of the cured composition, such as tensile strength, temperature resistance and elongation.
Various optional additives are used in amounts that do not exert a significant negative effect on the polymerization process or the desired properties of the compositions obtained with them.
Polymerizable compositions according to the invention can be used in a wide number of ways, including use as sealants, coatings, primers for surface modification of polymers and as molding resins. They can also be used as matrix resins in combination with mats made of glass and metal fibers, such as in the operations of the injection molding resins. They can be also used as sealants and caulking compounds, such as in the manufacture of e is actrices components and printed circuit boards. Predictably, they provide a polymerizable adhesive composition, which can glue a myriad of different substrates, including polymers, wood, ceramics, concrete, glass and primed metals. Other desirable related application is their use in ensuring the adhesion of coatings to substrates with low surface energy, such as polyethylene, polypropylene, polyethylene and polytetrafluoroethylene and copolymers. In this embodiment, the composition may be deposited on the surface of the substrate with surface modification to improve adhesion of the final coating to the surface of the substrate or introduced into the coating.
Compositions of the invention can be used in the coating process. In such applications, the composition may further comprise a carrier, such as a solvent. The coating may optionally contain additives well known to experts in the art for use coatings, such as pigments for coloring coatings, inhibitors and UV stabilizers. The composition can also be applied as a powder coating and may contain additives well known to experts in the art for use in powder coatings.
Compositions of the invention can also be used to modify the behavior of the displacement of the polymer molded parts, extruded film or a core subject. Compositions of the invention can also be used to change the functionality of the polymer particles by surface grafting of polymer chains on unmodified plastic substrate.
Polymerizable compositions of the invention, in particular, are used for bonding plastics or polymeric substrates with low surface energy, which have historically been very difficult to bond without the use of sophisticated technology of surface preparation, zagruntowane etc. Under substrates with low surface energy refers to materials which have a surface energy of 45 MJ/m2or less, more preferably 40 MJ/m2or less, and most preferably 35 MJ/m2or less. Included among such materials are polyethylene, polypropylene, Acrylonitrile-butadiene-styrene, polyamide, syndiotactic polystyrene, registereda block copolymers and fluorinated polymers such as polytetrafluoroethylene (Teflon), which has a surface energy of less than 20 MJ/m2. (The term "surface energy" other often used synonymous with the term "critical wetting tension"). Other polymers partly with higher surface energy, which can stick together songs image is the shadow, include polycarbonate, polymethyl methacrylate and polyvinyl chloride.
Polymerizable compositions of the invention can easily be used as two-component glue. The components of the polymerizable compositions are mixed, as is usually done when working with such materials. Complexdatatype agent is usually injected into the mixture in order to separate it from organoborane-amine complex, creating, thus, one component of two-component composition. Organoborane-amine complex initiator of polymerization provides the second component of the composition and is introduced into the first component shortly before it is desirable to use the composition. The complex can be introduced into the first component directly, or may be pre-dissolved in a suitable medium such as a reaction solvent or a monomer, i.e. methylmethacrylate or MMA/PMMA viscous solution, or in research considers non reactive diluent such as a solvent, just before the introduction of the first component.
It is desirable to keep the complexes separately from the monomers, oligomers or polymers to inhibit premature polymerization of monomers, oligomers or polymers. The complexes of this invention have significantly improved stability in the presence of monomers and in the absence of AG, the NTA of the destruction complex and thus, it can be stored with the polymerizable components of the composition.
For two-component adhesives, such as two-component adhesives of the invention, in order to most easily used in commercial and industrial environments, the volume ratio at which the two components are mixed, should be suitable integer. This facilitates the application of the adhesive with conventional commercially available transfer devices. Such transfer devices are shown in U.S. patent No. 4538920 and 5082147 and are available from the company Conprotec, Inc. (Salem New Jersey) under the trademark MIXPAC. Usually these transfer devices use a pair of tubular vessels arranged in series with each tube intended to receive one of the two components of the adhesive. Two pistons, one for each tube, at the same time moving forward (for example, manually or by using a manually triggered ratcheting mechanism) to discharge the contents of the tubes in a common hollow elongated mixing chamber, which may also contain a stationary mixer for easy mixing of the two components. Mixed adhesive is extruded from the mixing chamber to the substrate. Once the tubes are emptied, they can be replaced with fresh tubes, and the deposition process continues.
The ratio at which mixed the VA component glue, is governed by the diameter of the tubes. (Each piston is sized to enter the tube of fixed diameter, and the pistons are moving in the tubes with the same speed). One dispenser is often intended for use with a number of different two-component adhesives, and the plungers are sized to supply the two-component adhesive with proper mix ratio. The most common proportions of the mixture are 1:1, 2:1, 4:1 and 10:1, but preferably less than 10:1.
Component glue or polymerizable composition of the invention, which contains organoborane-amine complex, preferably has a temperature at or above room temperature. The resistance, as used here, means that organoborane-amine complex does not dissociate and does not initiate the polymerization of compounds with the olefinic unsaturation present in the composition. The resistance can be measured by determining the temperature at which the viscosity of the composition begins to increase. Preferably the temperature at which the viscosity increases, is above 40°C, more preferably above 60°C and most preferably above 80°C. the Increase in viscosity indicates that organoborane-amine complex dissociates, and initiated polymerization. In a variant, in which the composition is used in coding the STV glue, the adhesive is preferably shows a shear strength of the overlap of 100 psi (689 kPa) or more, more preferably 250 psi (1724 kPa) or more and more preferably 400 psi (2758 kPa) or more, in accordance with the following test method.
The adhesive components are mixed and applied to one or both of the substrate (1 inch x 4 inch x 1/8 inch (25.4 mm x 101,6 mm x 3.2 mm) polypropylene samples). The thickness of the adhesive bead can be controlled by adding a few wt.% glass beads with a diameter of 0.005-0,030 inch (of 0.13-0.76 mm). Samples match with the provision of overlapping substrates of 0.5-1.0 psig (161-645 mm2in the configuration for testing the shear splices. The samples are incubated together with metal clamps with continuous efforts and facilitate the removal of air bubbles from the adhesive during curing. Glued samples usually utverjdayut for at least 24 hours before installation in the setup for the tensile tests (Instron), equipped with a heating Cabinet. Samples tested at speeds of rolling clip of 0.05 inch/min (0.13 mm/min) and 0.5 inch/min (12.7 mm/min) at room temperature and 110°C, respectively. Maximum load (lbs) at fracture is fixed and the maximum stress (psi) calculated by dividing the load by the area of overlap (square is uimi).
Preferably the mixed two-component compositions of the invention have a suitable viscosity, providing application without dripping. Preferably the viscosity of the two separate components must be of the same order value. Preferably mixed compositions have a viscosity of 100 centipoise (0.1 PA·C) or more, more preferably 1000 SDRs (1,0 PA·C) or more, and most preferably 5000 centipoise (5,0 PA·C) or more. Preferably mixed compositions have a viscosity of 150,000 centipoise (150 PA·C) or less, more preferably 100000 SDR (100 PA·C) or less, and most preferably 50000 centipoise (50 PA·C) or less.
Packaging additives in the plastic substrate can affect the adhesion of the composition of the invention to a substrate. Found that some additives are not compatible with the active components of the compositions of the present invention. Specialist in the art can easily determine those additives that affect adhesion studies of adhesion of the sample to the substrate. Common additives that adversely affect adhesion, are Irganox 1076, inhibitor, available from the company Ciba Specialty Chemical Corporation, and potassium iodide. Common additives that have a negligible effect on the adhesion include inhibitor Irgafos 168, the inhibitor Tinuvin 328, the inhibitor Tinuvin 770, the inhibitor is Irganox 1010, available from the company Ciba Specialty Chemical Corporation, and calcium stearate.
The following examples are included for illustrative purposes only and are not intended to limit the scope of the claims. Unless otherwise indicated, all parts and percentages are given by weight.
Obtain adhesive compositions
Two-component adhesives receive, as described below. One component (hardener) includes organoborane-amine complex, mixed with the reaction solvent or research considers non reactive diluents. "Reactive diluent" means a material or compound that interact with some component of the resin, or acrylate (polymerization process), the initiator, or with both. Research considers non reactive diluents do not interact with components of the resin, such as glass spheres or low-boiling solvents. Low-boiling solvents are defined as solvents that boil at a temperature below the temperature of dissociation of organoborane-amine complex, i.e. the temperature at which the complex is divided. The amount of diluent is set by adjusting the viscosity and/or volumetric ratios (with obtaining the specified volume ratio of the component of the hardener and resin component). Other component (resin) is an acrylic resin with an initiator, such as West Africa the OIC acid or more preferably the isocyanate such as isophoronediisocyanate, which dissociates organoborane-amine complex in the interaction with the amine, when mixed with hardener. Acrylic resin is a mixture of methyl methacrylate (MMA) and polymethyl methacrylate (PMMA, molecular weight of 350,000 atomic units of mass), except as noted below. MMA and PMMA mix or rotate until the morning to mix PMMA with MMA. The resin contains 80/20 wt.% MMA/PMMA with the entered number complexdatatype agent (isocyanate), as shown by column IPDI (isophorondiisocyanate, unless specified otherwise). The obtained acrylic resin plus initiator preferably have a viscosity 1000-50000 CP (centipoise) (1,0-50 PA·). The above method provides the preferred formulation, where depolymerizes particles injected into the hardener component of two-component adhesive. This recipe gives a very long shelf life during storage (more than 5 weeks at 50°C).
The adhesive may be mixed in the desired ratio in the air, in the chamber or by using pressovannogo gun. Glue is applied to the samples in the form of ribbons with a width of 1 inch (25.4 mm) with an overlap of 1/2 inch (12.7 mm) and determine the adhesive strength as described previously. Polypropylene is used for low-temperature testing, and mixtures syndiotactic polystyrene (SPS)/nylon or e-coated metal sheets and the use for high-temperature tests. High temperature test was performed on the device for testing Instron, as described above. Sample tapes thermostatic in a desired temperature in a heating Cabinet installation Instron for at least 5 min before the test.
Polymerizable compositions of the invention containing organoborane-amine complex, receive and experience as described here.
The following abbreviations are used in tables.
Am usually indicates amines, as defined, which form a complex with borane.
RWMA denotes polybutylmethacrylate.
N denotes the hardener.
R represents the resin.
MORA denotes methoxypropylamine.
MeCl2 denotes methylene chloride.
Dytek A denotes 2-methyl-1,5-diaminopentane supplied by Dupont Co.
HMDI denotes hexamethylenediisocyanate.
TDI refers to 2,4-colorvision.
P-94 denotes a polymer diphenylmethanediisocyanate (MDI) brand PAPI-94 (trade mark of the company The Dow Chemical Company) with an average of 2.4 equivalents NCO/mol.
R-27 denotes a polymer diphenylmethanediisocyanate (MDI) brand PAPI-27 (trade mark of the company The Dow Chemical Company) with a 2.7 average equivalents NCO/mol.
UnRd denotes research considers non reactive diluent.
DMAPA indicates dimethylaminopropylamine.
TBB denotes tri-n-butylborane.
Emission spectra obtained for pure stands polymethylmethacrylate.
ACCESSORIES > stands CIS - or TRANS-from orangemen.
VS5500 denotes a hollow glass spheres manufactured by 3M Corporation.
Cabosil is a trademark of particles of colloidal silica company The Cabot Corporation.
APSi denotes aminopropyldimethylamine silica gel.
N2PPO 300 (or N2-300) denotes O-(2-aminopropyl-O'-(2-methoxyethyl)polypropylenglycol) (300 equals.).
IPDI denotes isophorondiisocyanate.
Polycap 300 denotes polycaprolactone with a molecular weight of 300.
N2PPO 115 denotes polypropylenglycol-bis-(2-aminopropyl) with an equivalent weight of 115 Amu (atomic mass units).
N2PPO 450 denotes polypropylenglycol-bis-(2-aminopropyl) with an equivalent weight of 450 AMA
N2PPO 1000 denotes polypropylenglycol-bis-(2-aminopropyl) with an equivalent weight of 1000 AME
DEA identifies diethanolamin.
E400 denotes ethylenebisstearamide diol having a molecular weight of 400.
T-9 denotes containing bivalent tin octanoate tin - catalyst for polymerization of urethane, available from the company Air Products Corporation.
N2-C9 denotes diaminononane.
RD denotes a reaction diluent.
*PAPI is a trademark of The Dow Chemical Company.
In the examples 1-71 curing agent is obtained by mixing the reaction diluent (RD), amine (Am) plus organoboron (TBB) as organoborane-amine complex and glass spheres VS5500 in mass zootoxin is s, as described below, typically use a total of 5 g of the above components. In the examples 72-91 curing agent is obtained by mixing organoborane-amine complex, the reaction diluent, the research considers non reactive diluent, Amin and VS5500 in portions, defined below. In the examples 87-91 curing agent obtained by mixing glass spheres VS5500, organoborane (TBB), the research considers non reactive diluent (UnRD), a reactive diluent (RD) and amine (Am) in the sub-samples defined below. All formulations used in these examples have the mix ratio resin : hardener 4:1 by volume, in addition to the examples 72-86, in which the mixing ratio hardener : resin are as defined in table 3, and C-2, which is 25:1. Adhesive is applied to a polypropylene substrate or e-coated metal, or other high-temperature substrate, as described above. Also the tables include values for the number of organoborane in the curing agent wt.% (wt.% TBB/N), the ratio of nitrogen atoms of the amine to boron atoms (N/B), the ratio of amine nitrogen plus other equivalents of active hydrogen to isocyanate reactive groups (ratio N/NCO), wt.% urea, as determined by weight only amine plus isocyanate, normalized to the total mass of the adhesive. Shear lap joints define the setup for the tensile tests, as described above. In the tables the results of digaetani overlap with the sign > mean that the destruction of the substrate takes place before the destruction of glue.
In the examples 1-53 all hardeners get with the total weight of the formulation 5,0, In examples 1-4, 20 wt.% the polymer solvent from the copolymer poly (methyl methacrylate)-polybutylmethacrylate having a molecular weight of 75000 AME, mixed with a reactive diluent. All of the examples 1-19 and 22-53 percentage TBB:N is 10 (TBB is 10 wt.% hardener). In examples 20 and 21 used by organoborane is triethylborane. The amount present of triethylborane is 0.27 g, and the percentage TEV:N is equal to 5.4. In the examples 37-41 the isocyanate is HMDI. In example 38 isocyanate is colorvision. In examples 39 and 42 isocyanate is a polymeric MDI available from the company The Dow Chemical Company under the trademark and designation PAPI94. In examples 40 and 43 isocyanate is a polymeric MDI available from the company The Dow Chemical Company under the trademark and designation PAPI27. In the examples 44-47 reaction diluent is given as the mass ratio of the components, values are in parentheses. In examples 48, 49 and 51 of the amine used as the reaction diluent is a solid polypropyleneoxide with amine end (molecular weight 1000), dissolved in liquid Amina at mass ratio of 1:1. In example 50 about the roadways to the ratio of solid N2-PPO and liquid Dytek A reaction diluent are 75 and 25%, respectively. In examples 52 and 53 of the reaction diluents are a mixture of the above amine and diaminononane at mass ratio of 1:1. In the examples, where the number VS5500 in the reaction diluent is not given specifically as a ratio (examples 25, 29, 49 and 51), the amount of glass is 40 wt.% of the total weight of the hardener. The density of the resin in table 1 is 1.
Table 1 shows the effectiveness of different classes of amines and amine mixtures with alcohols and research considers non reactive diluents. Table 1 shows examples of using different isocyanates as complexdatatype agent. The main classes shown here are polymer thickened amines, highly functional amines and aminogly, oligomeric diamines, mixtures of solid and liquid amines and mixtures of amines and alcohols and diols. Among the amines are structural variants, including monoamines, diamines, branched diamines, aliphatic cyclic amines, alkanolamines, diamines with primary and higher order amines and polyetheramines. The results in table 1 show that the compositions described provides excellent adhesion to plastic substrates.
Examples 54-73 carried out with different Koli is the EU ETS organoboranes TBB (tributylin) catalyst in the formulation of hardener and with different ratios of N/B. In these examples, the molar ratio of organoboron : amine is 1:0.5 mol for complex triethylborane Dytek A : amine and 1:1,4 for other complexes. In all examples, 54-77 and C1 reactive diluent contains 40 wt.% VS5500. Organoboranes used in examples 57, 62 and 68 to 71, is triethylborane (TEV).
|The reactions district|
|The shear strength of adhesive joints lapped at room temperature|
|The shear strength|
shear adhesive connection
cleave th soy-
|54||0,26||ACCESSORIES >||4,40||ACCESSORIES >||0,34||1,0||2,5||14||0,77||22,2||209||(1441)||800||(5516)|
|55||0,52||ACCESSORIES >||3,80||ACCESSORIES >||0,68||2,1||10,2||12,5||0,78||20,6||39||(269)||650||(4482)|
|56||0,778||ACCESSORIES >||3,20||ACCESSORIES >||1,02||3,1||6,1||11||0,79||18,9||>613||(>4226)||1900||(13100)|
|57||0,42||ACCESSORIES >||of 3.56||ACCESSORIES >||1,02||1,7||13,1||13||0,78||21,4||>654||(>4509)||1350||(9308)|
|58||1,035||ACCESSORIES >||2,61||ACCESSORIES >||1,36||4,1||4,1||10||0,77||17,7||388||(2675)||1400||(9653)|
|64||0,26||Dytek A||4,51||Dytek A||0,23||1,0||33,0||20||0,79||27,4||202||(1393)||450||(3103)|
|65||0,52||Dytek A||as 4.02||Dytek A||0,46||2,1||15,0||of 17.5||0,81||24,8||234||(1613)||600||(4136)|
|66||0,778||Dytek A||3,53||Dytek A||0,69||3,1||9,0||16||0,80||23,1||391||(2696)||600||(4137)|
|Continuation of table 2|
|67||1,035||Dytek A||3.04 from||Dytek A||0,92||4,1||6,0||14||0,81||20,9||350||(2413)||440||(3034)|
|68||0,14||Dytek A||4,78||Dytek A||0,08||0,6||34,5||20||0,82||27,6||31||(214)||550||(3792)|
|69||0,28||Dytek A||4,55||Dytek A||0,17||1,1||30,5||19,5||0,80||26,9||303||(2089)||400||(2758)|
|70||0,418||Dytek A||4,33||Dytek A||0,25||1,7||19,4||18,5||0,80||25,8||>551||(>3799)||575||(>3964)|
|71||0,558||Dytek A||4,11||Dytek A||0,33||2,2||13,7||of 17.5||0,80||24,7||>543||(>3744)||650||(4482)|
|C-11||0,778||ACCESSORIES >||3,20||ACCESSORIES >||1,02||4,69||6,1||72||80||0||Softening||--||30||(207)|
2The agent of the destruction complex and acrylic acid.
All the adhesives of the invention have good strength at room and high temperatures. With anicely example C-1 with a high ratio of N/B of the present invention, but using acrylic acid (AA) instead of the isocyanate as an initiator, gives poor adhesion at all temperatures. The second comparative example C-2 using a low ratio of N/B, the ratio of 25:1 and acrylic acid as an initiator, gives good adhesive at room temperature, but poor adhesive at an elevated temperature in comparison with the subject of the present invention. In the second comparative example, the complex gain adding of 1.36 mol MORA to 1 mol TBB. 4 wt.% this complex is added to the resin, consisting of 80 hours of MMA and 20 hours PMMA (Mw = 350,000) of 4 wt.% added acrylic acid. The mixture is applied on a polypropylene or e-coated metal substrates for testing at room temperature or 125°C, respectively. Provide curing of the adhesive within 3 days before the test.
Several adhesive compositions are given as described above. In the examples 72-77 reaction diluent and Amin both are isophorondiamine. In the examples 78-82 reaction diluent and Amin is the MORA, and research considers non reactive diluent is methylene chloride. In the examples 83-86 Amin and reaction diluent is Dytek A. Test shear adhesive lap joints carried out on plates made from a mixture of nylon-6 and syndiotactic polystyrene (SPS) at 125 and 150B0; C. For testing the shear adhesive lap joints in the examples 72-77 at 150°C and examples 78-82 at 125°C plates containing 30% PCA in nylon-6. In the examples 72-77 and 83-86 when tested at 125°C use plates containing 15% PCA in nylon-6.
Examples 72-86 show different aminobenzamide hardeners and the effect of changes in the ratio N/B at high temperature shear strength of adhesive lap joints. In each series the constant is the number of organoborane in Klee (variable in hardener), the amount of filler (VS5500) per 1 g of the liquid in the hardener and the ratio N/NCO. Unique in these examples is the mixing ratio (R/H, the resin/hardener), which varies in 2 of the series. The resin previously described. Figure 1 shows the increase in tensile shear adhesive lap joints as a function of increasing ratio N/B. Adhesives with a low ratio of N/B also have good durability due to the use of solvent and/or glass spheres VS5500 as teploreguliruth additives.
|R/H||N/B||% IPDI||N/NCO||% urine-|
|72||1,08||7,41||9,48||0,55||of 5.82||of 5.40||19,89||15,00||0,87||21,12||546(3765)|
|74||1,00||of 3.77||4,15||0,51||10,56||or 10.60||10,02||7,00||0,87||10,66||1084(7474)||483(3330)|
|75||0,96||2,13||1,74||0,49||18,02||18,80||to 4.98||3,30||0,88||the 5.25||966/6660)|
|83||to 2.06||5,71||5,79||0,72||14,40||7,00||to 9.93||14,50||0,86||18,39||882(6081)|
|85||1,90||to 2.29||0,86||0,67||33,30||17,50||of 2.51||3,40||0,86||of 4.66||745(5137)|
The adhesive formulation is obtained using resin component of MMA-PMMA as described previously, and a hardener component, as described in table 4, where research considers non reactive diluent is methyl methacrylate, the reaction diluent is isophorondiamine, hardener component contains 6.0 g of glass balls recipe VS5500 (example 91 uses 4.5 g VS5500 in the hardener and 1.5 g VS5500 in the resin), weight amine 1.2 g, volumetric ratio of resin : hardener is 4.0:1.0 and the ratio of amine equivalent : isocyanate equivalent is 0.8.
Figure 2 shows the rate of curing of a number of adhesives for different ratios of N/B. the Curves are cubic fits to the data time to observe graphically the time at which the adhesives otverzhdajutsja with a given strength of 50 psi (time cohesion). For these adhesives times cohesion is 39, 38, 25,6, 26,3, 27,7 min for ratios of N/B, 1,1, 3,4, 6,1, 9,9, respectively. Time cohesion even for low ratios of N/B is good thanks to the choice complexdatatype agent, component acrylic resin and teploreguliruth components.
|% TBB in H||N/B||%IPDI||% mo|
|88||2,3||3,4||2,1||the 15.6||3,0||of 5.4||7,6||38|
1. Two-component composition used to initiate curing of one or more polymerizable monomers, which otverzhdajutsja when exposed to free radicals, consisting of one component of organoborane-amine complex and the second component, isocyanate, which is able to destroy organoborane-amine complex, the de is equivalent to the ratio of the nitrogen atoms of the amine to boron atoms is more than 4.0:1 to 20.0:1.0 in.
2. Two-component composition for use as sealants, coatings, primers for surface modification of polymers and as molding resins containing
component 1 - a) organoborane-amine complex, in which the ratio of nitrogen atoms of the amine to boron atoms is more than 4.0:1 to 20.0:1.0 in, and
component 2 - b) one or more monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization free radical polymerization, and
(C) an effective amount of isocyanate, which causes dissociation of the complex, releasing the borane to initiate polymerization of one or more monomers, oligomers or polymers having olefinic unsaturation,
in which connection, which causes dissociation of the complex is contained separately from the complex to until initiation of polymerization is desired.
3. The composition according to claim 2, additionally containing a thickener, which represents a high molecular weight poly (methyl methacrylate), which can be entered in the amount of 10-60% relative to the total weight of the composition.
4. The composition according to claim 2, additionally containing elastomeric modifiers selected from the group consisting of chlorinated or chlorosulphurized polyethylene block copolymers of stiro the a and conjugated dienes, the grafted copolymer resin in an amount of 5-35% relative to the total weight of the composition.
5. The composition according to claim 2, additionally containing teploreguliruth material selected from the group consisting of volatile liquids that evaporate during the reaction as a result of absorption of heat released in the reaction, ceramic particles, glass beads, fluoropolymer powders or hollow spheres.
6. The composition according to claim 2, further containing a crosslinking agent selected from the group consisting of diacrylates, compounds with acrylate and isocyanate functionality of peroxides used in amount of 0.2-10% relative to the total weight of the composition.
7. The composition according to claim 2, additionally containing inhibitors such as phenols employed in the amount of 10-10000 hours/million in relation to the weight of polymerizable monomers.
8. The composition according to claim 2, additionally containing a catalyst for the reaction of compounds reactive towards isocyanate with isocyanatomethyl connection.
9. The composition according to claim 2 additionally containing a reactive or research considers non reactive diluent.
10. The composition according to claim 2, additionally containing research considers non reactive dyes, fillers, solvents.
11. The method of polymerization comprising the contacting of the components of the polymerizable composition according to claim 2 in such services is established, when one or more of monomers, oligomers or polymers undergo polymerization.
12. The method according to claim 11, which further comprises a stage of heating the composition to elevated temperature under such conditions that the amine and isocyanate can interact with.
13. Method of bonding two or more substrates together which contains
A. the contacting of the components of the composition according to claim 2 together under such conditions that initiate polymerization;
b. contacting the adhesive composition with two or more substrates;
c. the placement of two or more substrates such that the adhesive composition is located between two or more substrates, where they contact with each other, and
d. curing of glue in order to glue the two or more substrates together.
14. Method of bonding two or more substrates according to item 13, which further comprises heating the adhesive composition to a temperature that amine and isocyanate interacted advanced.
15. The modification of the polymer surface with a low surface energy by contact of the composition according to claim 2 with at least part of the polymer surface with low surface energy and the dissociation of the complex, the result of which is initiating the polymerization of the monomer, oligomers, polymers or mixtures thereof, so that the broken off the polymer is the polymer surface with low surface energy.
16. Method of coating composition to the substrate, which comprises contacting a composition containing
component 1 - a) organoborane-amine complex, in which the ratio of nitrogen atoms of the amine to boron atoms is more than 4.0:1 to 20.0:1.0 in, and
component 2 - b) one or more monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization free radical polymerization,
and heating the coating to a temperature of from 30 to 120°With initiating curing of the coating.
17. Method of coating substrates, which comprises the contacting of the components of the composition according to claim 2, contacting the exposed composition with one or more surfaces of the substrate and curing the coating composition.
18. The composition of the coating, which contains a composition according to claim 2.
19. The laminate containing at least two substrates, having located between the substrate and connected with each substrate composition according to claim 2.
20. Two-component polymerizable composition for use as sealants, coatings, primers for surface modification of polymers and as molding resins containing
component 1 - a) organoborane-amine complex and
component 2 - b) one or more monomers, oligomers or polymers having olefins is Yu unsaturation, capable of polymerization free radical polymerization, and
c) an effective amount of a compound that causes dissociation of the complex, which conserves the borane to initiate polymerization of one or more monomers, oligomers or polymers having olefinic unsaturation, in which connection, which causes dissociation of the complex was kept separately from the complex up until the initiation of the polymerization is not desirable, and
d) material, which regulates the heat of the polymerization reaction, so that supported the adhesion to the substrate, and the material can be located either component 1 or component 2, or both components
where the equivalent ratio of nitrogen atoms of the amine to boron atoms is more than 4.0:1 to 20.0:1.0 in.
21. The composition according to claim 20, further contain optional additives on p, 4, 6-10.
FIELD: building materials.
SUBSTANCE: invention relates to a hardening composition used in building industry. The composition comprising a polymer with two or more thiol groups per a molecule, compound with two or more isocyanate groups per a molecule, carbon black and calcium carbonate involves additionally a filling agent wherein silicic acid or silicate is the main component or organic filling agent wherein ground powdered carbon as the main component. The composition shows satisfactory stability in storing the basic compound and the hardening capacity even after storing the basic compound and, except for, it forms the hardened join with sufficient rupture strength limit, hardness and properties of barrier for gas. The composition comprises a hydrocarbon plasticizer and an organometallic compound preferably that provides highly effective hardening properties in combination with higher mechanical strength and properties of barrier for gas. Proposed hardening composition can be used as sealing material in manufacturing isolating glasses, frames, windows for transportation means, glues and covers.
EFFECT: improved and valuable technical properties of composition.
9 cl, 12 tbl, 11 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to polymer compositions including at least one polyurethane prepolymer A with isocyanate terminal groups obtained from at least one polyisocyanate with at least one polyol A1 and, if necessary, with at least one polyol A2. wherein A1 is linear polyoxyalkylenepolyol with unsaturation degree ,less than 0.04 m-equ/g; A2 is polyol, which is present in amount 0-30%, preferably 0-20%, in particular 0-10% based on total amount A1+A2; and at least one polyaldimine B. Composition is a mixture of polyurethane prepolymer A with polyaldimine B. In absence of moisture, such compositions are stable on storage. When being applied, such compositions are brought into contact with moisture, after which polyaldimines are hydrolyzed into aldehydes and polyamines, and polyamines react with polyurethane prepolymer containing isocyanate groups. Products obtained from such composition possess very wide spectrum of properties, including tensile strength varying within a range from 1 to 20 MPa and ultimate elongation above 1000%. Composition may be used as glue, hermetic, coating, or facing.
EFFECT: expanded possibilities of polyurethanes.
3 cl, 7 tbl, 34 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to compositions based on polyols and high-molecular weight diisocyanates with low monomer content as well as to a method for preparation of indicated compositions as binders for reactive glues. In particular, invention provides reactive polyurethane composition based on polyols and high-molecular weight diisocyanates prepared by reaction of diols having average number molecular weight mot higher than 2000 with monomeric diisocyanates having molecular weight not higher than 500. Thus obtained high-molecular weight diisocyanates have maximum monomer content 10%. Invention also describes a method for preparation of indicated composition. Thus obtained compositions are used as glues/hermetics imparting improved adhesion characteristics and having significantly reduced contents of health-detrimental monomeric diisocyanates having molecular weight below 500. For instance, resistance to detachment of film attached to surface using claimed glue is 4.3 N/mm, heat resistance lies at a level of 148°C, and frost resistance below -30°C.
EFFECT: improved adhesive characteristics.
13 cl, 3 tbl, 20 ex
SUBSTANCE: invention relates to compositions based of synthetic high-molecular weight compounds and, in particular, to composition comprising polyurethane-based preparation DESMOCOLL, perchlorovinyl resin, epoxide resin, aliphatic-series polyamine, and polar organic solvent.
EFFECT: enabled retention of high elasticity of glue joint and considerably increased gluing strength for siloxane-coated materials, kapron fabrics, and glass cloth.
FIELD: gluing compositions.
SUBSTANCE: invention relates to a composition that comprises polypropylene glycol glycerol adipinate as a polyester, monophenyl urethane, stabilizing agent, phenolformaldehyde resin, p-dinitrobenzene as a polymerization activating agent, urotropin as a cross-linking agent, a mixture of cyclohexanone, xylene and methyl ethyl ketone as a solvent. The composition can be used in applying on cold and hot surface. Invention is used for teasing articles made of industrial rubber, in preparing monocomponent polyurethane glues for teasing rubber surfaces by electrostatic flocculation method and can be used in industrial rubber and automobile industries. Invention provides conferring thermal stability, reducing vulcanization time and enhancing adhesion strength.
EFFECT: improved and valuable properties of composition.
FIELD: rocketry; development of a composition of binding substance for manufacture of the brush type products.
SUBSTANCE: the invention is pertaining to the field of rocketry, in particular, to development of a composition of binding substance for manufacture of the brush type products. The composition contains, in mass %: hydroxyl-containing polybutadiene rubber - 31.0-33.0; zinc oxide or carbon technical - 7.4-8.0; 1.4- butyleneglycol - 0.7-0.8; trimethylolpropane - 0.08-0.1; transformer oil - 5.2-5.6; stannous dibutyldilaurate - 0.013-0.036; a hardener - oligodiene urethane prepolymer in a combination with 20 % solution of triphenylmethanetriisocyanate in dichlorethane or 27 % solution of triphenylmethanetriisocyanate in ethylacetate with the contents of isocyanate groups of 3.5-4.5% and 53.0-55.5%. The technical result of the invention - manufacture of the composition of binding substance with the high mechanical, binding and operational characteristics and with provision of serviceability of the finished products in the range of temperatures from plus 50°C to minus 50°C at action of high loadings.
EFFECT: the invention ensures production of the binding substance composition with high mechanical, binding and operational characteristics and serviceability of the finished products at the temperatures of plus 50°C - minus 50°C at action of high loadings.
FIELD: rocket engineering and adhesives.
SUBSTANCE: invention provides composition for attaching solid fuel charge to rocket engine body, said composition being constituted by oxidant, fuel, binder based on synthetic rubber plasticized with mineral plasticizer, transformer and vaseline oils, curing additives, and catalysts. More specifically, glue composition contains urethane rubber with intrinsic viscosity [η] = 0.3-1.3 Dl/g and weight percentage of double bonds 0.5-2.5%, curing agent of the type of dinitrile oxides reactive to double bonds, and solid epoxide resin from diphenylolpropane and epychlorhydrin as active filler.
EFFECT: increased resistance to diffusion of oils from fuel and optimized curing regime regarding curing temperature and duration synchronization.
9 tbl, 7 ex
FIELD: mechanical rubber goods, automotive industry, adhesive composition based on chlorine-containing rubber.
SUBSTANCE: claimed composition contains chlorinated natural rubber, aromatic dinitroazo compound, epoxy resin, fillers, and antioxidants. Said composition is characterized in that it contains 2,3-dichlorobutadiene-1,3/chloroprene copolymer as polymeric carrier and additionally phenol-formaldehyde resins of phenol- and resole-type, wetting agent and mixture of xylene or toluene with methylethylketone as solvent.
EFFECT: universal composition with increased adhesive resistance.
FIELD: polymerization processes.
SUBSTANCE: invention, in particular, relates to production of random butadiene/isoprene copolymers and consists in the following. Random butadiene/isoprene copolymer is obtained via interaction of butadiene and isoprene in presence of catalytic system. The latter is a system based on at least one conjugated diene monomer, organic phosphorus acid salt with one or more rare-earth metals, alkylation agent consisting of alkylaluminum of formula AlR3 or HAlR2, and a halogen donor represented by alkylaluminum halide. Above-mentioned salt is present in suspension of at least one inert saturated aliphatic or alicyclic hydrocarbon solvent included in said catalytic system. Molar ratio of alkylation agent to salt of one or more rare-earth metal(s) varies between 1:1 and 8:1. Reaction is conducted in inert hydrocarbon solvent or without solvent. Random butadiene/isoprene copolymer obtained according to claimed method is such in which butadiene and isoprene units are in reality randomly alternated in accordance with Bernoulli formula. Glass transition temperature TGexp of the copolymer as measured by differential enthalpimetric analysis satisfies following inequality: -0.05 = (TGexp - TGth) = 0.05, wherein TGth represents theoretic glass transition temperature of the copolymer calculated in terms of Fox equation: 1/TGth = α/ Tg(br) + β/ TG(ir), wherein Tg(br) and TG(ir) represent, respectively, glass transition temperatures measured by differential enthalpimetric analysis for polybutadiene and polyisoprene synthesized with the aid of indicated catalytic system, wherein α and β are, respectively, weight fractions of butadiene and isoprene units. Random butadiene/isoprene copolymers have elevated content of cis-1,4 bonds.
EFFECT: enabled production of copolymers, which have real random distribution of butadiene and isoprene units.
2 cl, 2 tbl
SUBSTANCE: invention relates to method for production of polyisoprene with increased content of cis-1,4-sequences from isoprene-enriched C5-cut from vapor-phase naphtha cracking. Claimed method includes interaction of isoprene-enriched C5-cut from vapor-phase naphtha cracking in presence of catalytic system. Isoprene content in said cut is 30-95 mass %, and catalytic system is based on at least one conjugated diene monomer, salts of one or more rear earth metals with organophosphoric acid, alkylation agent, namely aluminum alkyl of formula AlR3 or HalR2 and halogen donor namely halogenated aluminum alkyl. Abovementioned salt is in slurry, in at least one inert hydrocarbon solvent representing aliphatic or alicyclic hydrocarbon containing in said catalytic system, wherein molar ratio of alkylation agent to rear earth metal salt is in range of 1-5.
EFFECT: isoprene polymerization with high catalytic activity; product having increased content of cis-1,4-sequences.
21 cl, 3 tbl, 3 ex
FIELD: polymerization reaction catalysts.
SUBSTANCE: catalyst, which may be useful in production of cis-1,4-polymers and cis-1,4-copolymers in synthetic rubber industry, is prepared by mixing, in hydrocarbon solvent, rare-earth element compound, conjugated diene, alkylation agent, and halogen source, said halogen source being aryldimethyl halides or their mixtures with alkylaluminum chlorides. Process is carried out at molar ratio 1:(1-100):(10-100):(0.3-3), respectively.
EFFECT: increased catalytic activity and enabled production of low-dispersity polymers characterized by good performance properties resulting in a high level of physicochemical characteristics of rubber manufactured from these polymers.
2 cl, 1 tbl
FIELD: chemistry of polymers, chemical technology, catalysts.
SUBSTANCE: invention relates to a method for preparing a catalyst used in polymerization of butadiene and copolymerization of butadiene with coupled dines. Method involves interaction of components comprising the compound of rare-earth element, diisobutyl aluminum hydride, triisobutyl aluminum, alkyl aluminum halide and coupled diene. Firstly, method involves mixing rare-earth element and coupled diene solutions with diisobutyl aluminum hydride solution, and the mixture is kept for 10-30 min at stirring, and then triisobutyl aluminum and alkyl aluminum halide solutions are added. After mixing all components the mixture is kept for 10-15 h in the following mole ratio of components: rare-earth element : diisobutyl aluminum hydride : triisobutyl aluminum : alkyl aluminum halide : coupled diene = 1:(3-12):(6-12):(1.5-3):(2-20), respectively, wherein rare-earth element carboxylate or alcoholate is used as a source of rare-earth element. Invention provides preparing the high-effective catalyst allowing preparing highly stereoregular polybutadiene and butadiene copolymer with the couples diene with simultaneous reducing the range of molecular-mass disposition by 3-3.5 times.
EFFECT: improved preparing method.
FIELD: polymerization catalysts.
SUBSTANCE: catalyst preparation involves interaction of rare-earth element compound, conjugated diene, and diisobutylaluminum hydride followed by ageing of reaction mixture for 10-30 min, adding tetraisobutyl-dialumoxane and alkylaluminum hydroxide at molar ratio 1:(2-20):(3-12):(6-12):(1.5-3), respectively, and ageing resulting mixture for 10-15 h. Diene utilized is in the process is pyperilene or isoprene and rare-earth element compound is rare-earth element carboxylate or alcoholate. Catalyst can, in particular, find use in production of cis-1,4-polydienes.
EFFECT: achieved preparation of high-efficiency catalyst enabling production of highly stereospecific polybutadiene or butadiene/isoprene or butadiene/pyperilene copolymers at narrower molecular mass distribution.
FIELD: polymerization catalysts.
SUBSTANCE: catalysts, which may, in particular, be used in production of cis-1,4-homopolymers and cis-1,4-copolymers in synthetic rubber industry, are prepared by reaction of rare-earth element compound and conjugated diene in hydrocarbon solvent with preliminarily formed complex, the latter being prepared by chlorination agent-alkylation agent-Lewis base triple interaction.
EFFECT: increased activity and stereoselectivity of catalyst.
10 cl, 1 tbl, 20 ex