New poly(monoperoxyphthalate)


C07C409/38 - the ; OO group being bound between a CO group and a carbon atom, not further substituted by oxygen atoms, i.e. esters of peroxy acids

 

(57) Abstract:

The invention relates to new compounds, such as poly(monoperoxyphthalate) the overall structure AND

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where R, R1and n are defined in the summary of the invention, such as 1,1,1-Tris(tert-butylperoxycyclohexyl)ethane, intermediate compounds for their production, and methods for their production and application. Monoperoxyphthalate useful for initiating polymerization ethylenedeamine monomers, in particular styrene, curing unsaturated polyesters and modification of molecular weight of polymers by crosslinking or regulated degradation chain. 2 C. and 16 h.p. f-crystals, 6 PL.

Background of the invention

a) the technical Field to which the invention relates

The present invention relates to new compounds classified in the field of chemistry as poly(monoperoxyphthalate) patterns:

< / BR>
(definition of n, R and R1given in section " Summary of the invention), to processes for their preparation and their use and to intermediate compounds used in the methods of production.

In the industry of polymers there is a need to effektivnih, as the styrene with higher performance while maintaining the molecular weight of the polymer and the physical properties of the polymer, for example mechanical properties tensile. Usually the more active free-radical initiators and increasing the temperature of polymerization to increase the rate of production of polymers (e.g. polystyrene) lead to the desired increase in performance, but also entail undesirable consequences, such as reducing the molecular weight of the polymer and the deterioration of the physical properties of the polymer. Reducing the temperature of polymerization, reducing the used amount of the initiator and the use of less-active initiators generally provide an increase in the molecular weight of the polymer, but this reduces performance. In 80-ies there was progress in the field of polymerization of styrene. The use of diphenoxyethane, such as 1/1-bis(tert-BUTYLPEROXY)cyclohexane, as the initiators instead of conventional initiators such as Dibenzoyl peroxide and tert-butyl peroxybenzoate, in industrial processes for the polymerization of styrene resulted in increased molecular weight and increase in the production of polystyrene. These applicants have further developed which can be used as initiators for polymerization ethylenedeamine monomers to obtain a polymer (for example, polystyrene) having significantly higher molecular weight while maintaining or increasing the speed of polymerization, or by obtaining polymers with much higher speeds polymerization with preservation of molecular weight and that the compounds of the present invention is better than diphenoxyethane, such as 1,1-bis(tert-BUTYLPEROXY)cyclohexane. Thus, the new poly(monoperoxyphthalate) of the present invention is able to satisfy the needs of the industry of polymers related to polymerization processes.

In the production of polyesters, too, there is a need in the free-radical initiators, curing unsaturated polyester resins faster and/or at lower temperatures. New poly(monoperoxyphthalate) of the present invention is also able to satisfy this need of the industry of polymers.

b) Description of the prior art

In U.S. patent 3652631 (issued by PPG March 28, 1972) discloses bis(monoperoxyphthalate) 1

< / BR>
(where R1and R3represent alkyl having up to 10 carbon atoms, optionally substituted with halogen or nitro group, and R2represents a bivalent from tert-butylhydroperoxide, tert-AMYLPEROXY, or tert-helsinkiproposed and bis(chloroformate) and the use of these compounds for the polymerization of monomers, such as styrene. U.S. patent 3652631 covers a bis(monoperoxyphthalate), 1,5-bis(tert-butylperoxycyclohexyl)-3-oxa-pentane. The applicants of the present invention have found that poly(monoperoxyphthalate) patterns And are new and the best initiators in the polymerization of styrene than 1,5-bis(tert-butylperoxycyclohexyl)-3-oxapentane, as they gave the polystyrene with a significantly higher molecular weights under the same conditions of polymerization.

In U.S. patent 4136105 (issued by Pennwalt Corp. January 23, 1979) revealed O-alkyl OO-tert-excellentperformance 2

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(where n represents an integer from 1 to 4, preferably 1; when n = 1, R is selected from alkyl with 1-16 carbon atoms, cycloalkyl with 5-12 carbon atoms, aryl with 6-14 carbon atoms, aralkyl with 7-14 carbon atoms, alkenyl with 3-10 carbon atoms, cycloalkenyl with 5-10 carbon atoms and quinil with 3-14 carbon atoms; when n = 2, R is selected from alkylene with 2-12 carbon atoms, cycloalkyl with 4-12 carbon atoms, arylene with 6-14 carbon atoms, Alcanena with 2-12 ug is1XR1and R2YR2- where R1is alkylene with 2-6 carbon atoms, R2is phenylene, X is-O - or-S - and Y is-O-, -S-, -CH2- or(CH3)2-; when n = 3, R represents R3C(CH2-)3, -CH(CH2-)2and CH2CH(-)CH2CH2CH2CH2- where R3represents alkyl with 1-5 carbon atoms; and when n = 4, R represents(CH2-)4and the use of these compounds for initiating polymerization of vinyl monomers and curing of unsaturated polyesters. This patent covers the Tris - and tetrakis(mono-tert-octylphenoxypoly) was obtained from tert-activedatabase, but does not reveal new poly-(monoperoxyphthalate) of the present invention, which is obtained from tert-butyl and tert-AMYLPEROXY.

In U.S. patent 5314970 (issued by Elf Atochem may 24, 1994) revealed OO-t-alkyl O-polycaprolactones, that is consistent with the locked end OO-tert-alkilirovannami groups 3, obtained from tert-alkylhydroperoxides and chloroformiate

(A-X)m-R-(-X'-B)n< / BR>
where it is

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In is

< / BR>1and R2are the same or different and represent alkyl with 1-4 carbon atoms, R3represents alkyl with 1-12 carbon atoms or quinil with 2-12 carbon atoms, y represents an integer from 0 to about 10,000, x is an integer from 4 to about 22000, (y)(m)+(x)(n) represents an integer from 4 to about 22000, X and X' are independently selected from-O -, or-N(R4-), and R4represents hydrogen, substituted or unsubstituted aliphatic with 1-20 carbon atoms, substituted or unsubstituted alicyclic from 5-18 carbon atoms, a substituted or unsubstituted aromatic with 6-14 carbon atoms and substituted or unsubstituted analiticheskii with 7-22 carbon atoms, and R represents a substituted or unsubstituted aliphatic, alicyclic, aromatic or analiticheskii radical, biradical, triradical or tetradecyl),

polycarbonate with terminal hydroxy groups and the use of these compounds for initiating polymerization of the vinyl monomer for curing unsaturated polyesters to obtain polycaprolactone block copolymers, crosslinking of polyolefins, for curing elastomers, for modifying polypropylene, for Ÿ graft polyols.

The only monoperoxyphthalate, which were disclosed in the examples, were bis(tert-butylanthraquinone) and bis(tert-amiloridesensitive) derived from diols. The only usefulness disclosed in the examples, and usefulness, highlighted in the abstract, the description and the claims, was the use of bis(monoperoxyphthalate) to obtain polycaprolacton-polystyrene block copolymers and graft copolymers for use as an agent that improves the compatibility, for mixtures of polymers. Since the most effective block copolymers for interoperable mixtures of polymers block copolymers with larger block segments, the most preferred poly(e-caprolactone) were poly(e-caprolactone) with dihydroxycinnamic terminal groups with a molecular mass of approximately 3000-15000 (U.S. patent 5314970, column 12, lines 30-33). The original materials of the present invention, related to poly(e-caprolactone) with hydroxyl end groups, is limited to poly(e-caprolactone) with integral polyhydroxybutyrate, except in special cases, when new peroxidation bis(monoperoxyphthalate) is produced by the interaction of bis(haloge the si)IntelliProtector or 1,1,4-trimethyl-4-(tert-AMYLPEROXY)IntelliProtector. In addition, polyhydroxylated source materials (i.e., diols, trioli or higher polyols) for compounds of the present invention should have a molecular weight less than about 1000, less than about 1000, less than about 1300, respectively.

U.S. patent 5314970 does not move forward in the field of polymerization of styrene using the proposed in patent bis(monoperoxyphthalate). Proposed in U.S. patent 5314970 compound is bis(tert-butylanthraquinone obtained from TONE200. The applicants of the present invention have found that the new poly(monoperoxyphthalate) patterns And were the best initiators in the polymerization of styrene, as they gave the polystyrene with a significantly higher molecular weights under the same conditions of polymerization than that obtained using bis(tert-butylanisole-carbonate) of the TONE200.

In U.S. patent 5455321 (issued by The Dow Chemical Company October 3, 1995) disclosed a method of obtaining nonoverridable aromatic polymer (e.g. polystyrene) having a molecular weight above 275000, which method comprises the polymerization nonoverridable aromatic monomer (e.g. styrene) with the purpose to branching, having a structure:

R'(CO)nOOR)m,

where n represents 0 or 1, m is 3-6, R' represents a multi-functional organic radical having up to 25 non-hydrogen atoms, and R represents a C1-15tertiary alkyl or C7-15tertiary kalkilya group, and

b) 10-2000 ppm of one or more organic reducing gelation agents selected from the group consisting of i) mercaptans, terpenes, haogenplast and kalogeropoulou having up to 20 carbon atoms, (ii) recycle liquid obtained by removing the volatile products from the polymerized mixture of polymers, and (iii) mixtures of organic agents that reduce the gelation of i) and ii). The preferred initiator of free-radical polymerization with branching was 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)-propane:

< / BR>
Other initiators of free-radical polymerization with a fork, disclosed in this patent, were complex three-tert-alkalemia ester of 1,3,5-benzotrichloride, complex Tetra-tert-alkalemia esters 1,2,4,5-benzylaminopurine and 2,4,6-tri-tert-alkylperoxy-1,3,5-triazine, 2-(4-isopropylphenyl)-2-propyl tert-alkylperoxide, tert-alkyl 4-isopropanolamine and monoperoxyphthalate. In U.S. patent 5455321 not revealed any new poly(monoperoxyphthalate) of the present invention, no new methods for their use in the manufacture of polymers.

In U.S. patent 5266603 (issued by Huels Aktiengesellschaft November 30, 1993) disclosed a method of obtaining a foaming homopolymers and copolymers of styrene by a) preparation of an aqueous suspension of styrene monomer and peroxide initiator system containing at least one aliphatic or cycloaliphatic diphenoxyethane (for example, 2,2-bis(tert-BUTYLPEROXY)butane and 1,1-bis(tert-BUTYLPEROXY)cyclohexane) or monoisocyanates initiator (e.g., OO-tert-butyl O-(2-ethylhexyl)nonoperational or OO-t-amyl O-(2-ethylhexyl)nonoperational) and the peroxide initiator having a shorter half-life than aliphatic or cycloaliphatic diphenoxyethane or monoisocyanates initiator (for example, Dibenzoyl peroxide), (b) heating the stirred suspension at a temperature of from 80 to 100oWith over a first time period for the implementation of the initial polymerization, (C) adding to the stirred suspension3-6hydrocarbon dispersant, (d) raising the temperature of the resulting suspension to the receipt of expandable polystyrene. In this patent does not use any bis-or Tris-or higher poly(monoperoxyphthalate), and use only mono-(monoperoxyphthalate), such as OO-tert-butyl O-(2-ethylhexyl)nonoperational or OO-t-amyl O-(2-ethylhexyl)nonoperational.

In General, in the above-described materials poly(monoperoxyphthalate) of A structure not disclosed.

(C) Definition

Diol is defined as the structure of the R(-OH)2where R represents biradical, such as R(-)2. Triol is defined as the structure of the R(-OH)3where R represents triradical, such as R(-)3. The polyol is defined as the structure of the R(-OH)nwhere R represents polyradical, such as R(-)nand n represents the integer 2. Tetraol is defined as the structure of the R(-OH)4where R represents tetradecyl, such as R(-)4.

When in the General formula or the structure of the generalized functional group or index, such as R, R1, R2, x, n and so on, appears more than once, their values do not depend on each other.

Summary of the invention

In accordance with the present invention in its first aspect related to the connection, it is proposed poly(nonoperational) structures of the radicals with 4-12 carbon atoms, 1,1,4-trimethyl-4(tert-BUTYLPEROXY) penciling radical, 1,1,4-trimethyl-4(tert-AMYLPEROXY) penciling radical, tert-cycloalkyl radical with 6-10 carbon atoms, tert-Uralkalij radicals from 9 to 13 carbon atoms and 3-methyl-1-butyn-3-yl and 3-methyl-1-pentyn-3-yl, provided that:

when R1selected from 1,1,4-trimethyl-4(tert-BUTYLPEROXY) penciling radical and 1,1,4-trimethyl-4(tert-AMYLPEROXY) penciling radical, n can have the value 2;

when n = 2, R represents biradical selected from alkylene with 2-12 carbon atoms, Alcanena with 4-8 carbon atoms and biradical structures (n) and (o)

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where R9is alkilinity biradical with 2-8 carbon atoms;

when n = 3, R represents triradical selected from 1, 3, 5-cyclohexatriene, R2C(CH2-)3, -CHR2H (-)CH2and structures (a), (b), (C), (d) and (e),

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< / BR>
< / BR>
< / BR>
< / BR>
where R2selected from hydrogen and an alkyl radical with 1-6 carbon atoms, R3is triradical selected from the group consisting of a2C(CH2-)3, -CHR2CH(-)CH2and structures (a) and (b), R4and R5are the same or different and selected from hydrogen and alkyl Radica 2 to 8, and r, s and t are integers from 0 to 6 with the proviso that the sum of r, s and t is from 3 to 18, and when n = 4 to 8, R represents polyradical selected from C(CH2-)4and structures (f), (g), (h), (i), (j), (k) and (l)

< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
where R6is tetradecyl selected from C(CH2-)4and structures (f), R7is biradical selected from alkylene with 2-6 carbon atoms and 1,2-, 1,3-and 1,4-phenylene, R8is octanediol on the basis of sucrose having the structure (m)

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p represents an integer from 1 to 3, v is an integer from 0 to 5 with the proviso that the sum of v, x, y and z is from 3 to 10, and q is an integer from 0 to 4 with the proviso that the sum of q, r, s and t is from 2 to 16, and with the additional proviso that when R is R3C(CH2-)3structure (b) or(CH2-)4, R1is not tert-actiom; and a new poly(nonoperational) patterns synthesized from A diol, triol or higher polyol structure AA:

< / BR>
having a molecular weight less than about 1000, less than about 1000, or less than about 1300, respectively.

In accordance with the present invention in ogrodowa aspect with is selected from 1,3,5-cyclohexatriene, R2C(CH2-)3, -CHR2CH(-)CH2and structures (a), (b), (d) and (e) defined above.

In accordance with the present invention in the second ogrodowa aspect of the connection features connection patterns And" where in the structure And, when n = 3, R is as defined above for the first photodamage aspect of the present invention, and when n = 4 to 8, R represents polyradical selected from C(CH2-)4and structures (f), (g), (i), (j), (k) and (1) defined above.

Compounds according to the first aspect of the present invention have physical properties that are characteristic of amorphous solids or viscous liquids, and these solids have the color from white to pale straw, and these liquids are painted in the color of light straw. Solids have limits melting, and all connections have infrared spectra and the content of active oxygen of the peroxide, which clearly confirm the need for patenting of these structures.

Compounds according to the first aspect of the present invention is inherently suitable for practical use as initiators for polymerization ethylenedeamine monomers, in particular styrene, E. polymers, elastomeric polymers and mixtures of such polymers.

In accordance with the present invention in its first aspect of the method, the proposed method of free-radical-initiated modification of the substrate selected from the group consisting of Ethylenediamine monomers and polymers susceptible to free-radical induced modification of molecular weight, which includes the processing of these substrates under conditions effective to initiate free-radical-induced modification of the above substrates, one or more compounds of structure (A) in initiating effective amounts.

Specifically, you can call the following processes of free-radical induced modification of molecular weight:

a) polymerization ethylenedeamine monomers (such as styrene, ethylene, allylchloroformate (ADC ADC) and the like, which are known in the art as compounds that are susceptible to such polymerization), optionally in the presence of unsaturated elastomer such as polybutadiene, polyisoprene and the like, useful, as is known in the art, in the case of the presence of the e and curing thermoplastic and elastomeric polymers; and

e) modifying the molecular weight of polyolefins.

In accordance with the present invention in the second aspect related to the method proposed method of free-radical initiated polymerization ethylenedeamine monomers (such as styrene, ethylene, allylchloroformate (ADC ADC), and the like), which are known in the art as compounds that are susceptible to such polymerization, optionally in the presence of unsaturated elastomer such as polybutadiene, polyisoprene and the like), useful as it is known in the art, in the presence of such polymerization processes, under conditions effective for initiating the free-radical induced polymerization with one or more compounds of the structure And in combination with other initiators of free-radical polymerization selected from the group consisting of nonoperation and diperoxide (such as diazepamonline, diphenoxyethane, complex peroxidase, monoisostearate and dialkylamide), in initiating effective amounts.

A detailed description of the preferred options

New poly(monoperoxyphthalate) patterns And Sposaitalia one or more tert-alkylhydroperoxides structure B

R1-OOH

c poly(halogenfree) structure at a temperature of from -30 to 50oWITH,

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where R, R1and n are such as defined for structure A, optionally in the presence of an inorganic or organic base and optionally in the presence of one or more solvents.

Non-limiting examples of suitable optional bases include triethylamine, tributylamine, N, N-diisopropylethylamine, 2,2,6,6-tetramethylpiperidine, N, N-dimethylaniline, N,N-dimethylaminopyridine, 2,4,6-koledin, urea, tetramethylrhodamine, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate and trisodium phosphate.

Non-limiting examples of suitable optional solvents include pentane, hexane, heptane, dodecane, a mixture of white spirits odorless, toluene, xylenes, cumin, methylene chloride, ethyl acetate, 2-ethylhexanoate, isobutyl-isobutyrate, dimethyladipate, dimethylsuccinic, dimethylglutaric (or mixtures thereof), dimethylphthalate, dibutyl phthalate, benzylbutylphthalate, diethyl ether, methyl tert-butyl ether (MTBE, MTBE), 2-ethoxyethylacetate, tetrahed sanitatio with poly(halogenfree) structure C, include tert-butylhydroperoxide, tert-AMYLPEROXY, 2-methyl-2-pentylcyclohexyl, 3-methyl-3-pentylcyclohexyl, 3-methyl-1-butyn-3-imagereference, 3-methyl-1-pentyn-3-imagereference, 2-methyl-2-exercitatione, 1,1,3,3-tetramethylbutylamine, 1,1,4-trimethyl-4(tert-BUTYLPEROXY)intellitrace, 1,1,4-trimethyl-4(tert-AMYLPEROXY)intellitrace, 1-methyl-1-cyclohexylacetophenone, parameterizations-cumylhydroperoxide, 4-methyl-cumylhydroperoxide, 3-methyl-cumylhydroperoxide and diisopropylethylamine.

Non-limiting examples of suitable poly (halogenfree) structure C, which can be subjected to interaction with hydroperoxides patterns, include 1,1,1-Tris(chlorocarbonylsulfenyl)ethane, 1,1,1-Tris (chloro-carbonyloxy)-propane, 1,1,1-Tris(chlorocarbonylsulfenyl)butane, 1,2,3-Tris(chlorocarbonate)propane, 1,2,3-Tris(chlorocarbonate)hexane, 1,2,3-Tris(chlorocarbonate)heptane, 1,2,4-Tris(chlorocarbonate)butane, 1,2,6-Tris(chlorocarbonate)hexane, 1,3,5-Tris(chlorocarbonate) cyclohexane, tetrakis(chlorocarbonylsulfenyl)methane, 1,2,3,4-tetrakis(chlorocarbonate)butane, 1,1,1,5,5,5-hexa(chlorocarbonylsulfenyl)-3-oxapentane and 1,1,1,5,5,9,9,9-Oct (chlorocarbonate onformity) structures D and E:

< / BR>
< / BR>
which are derived from polycaprolactone and-tetraols (patterns F and G, respectively):

< / BR>
< / BR>
such as those that produce f. Union Carbide Corporation and sold under the trademark TONEfor example TONE0301, TONE1303, TONE0305, TONE0310 and TONE4411, and Tris - and tetrakis(chloroformate) structures H and I:

< / BR>
< / BR>
which are derived from polyetherdiols and-tetraols (patterns J and K, respectively):

< / BR>
< / BR>
some of which produces BASF Corporation under the trademark PLURACOL; where R4represents methyl and R5represents hydrogen, such as PLURACOLGP-730, PLURACOLTR-740, PLURACOLPeP 450, PLURACOLPeP 550 and PLURACOLPeP 650, and others, which are produced by Dow Chemical Company under the trademark VORANOLsuch as the structure of J, where R4and R5represent hydrogen, such as VORANOL234-630, and some others, which are produced by Arco Chemical Company under the trademark ARCOLsuch as the structure of J, where R4represents methyl and R3represents hydrogen, such as ARCOLLG-650 and ARCOL/SUP> specified by the manufacturers and are given in table.I.

When R1patterns And represents 1,1,4-trimethyl-4(tert-BUTYLPEROXY)pentelenyi radical or 1,1,4-trimethyl-4(tert-AMYLPEROXY)pentelenyi radical and n = 2, to obtain polyperoxides patterns And you can use bis(halogenfree), which is derived from diols. Non-limiting examples dolovich predecessors bis(halogenfree) include ethylene glycol, 1,2-and 1,3-propylene glycols, 2,2-dimethyl-1,3-propandiol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropyleneglycol, 1,4-cyclohexanedimethanol, diols TONE and others.

Define R3, R6, q, r, s, t, v, x, y and z are given in section a Brief summary of the invention.

The above poly(halogenfree) can be obtained by interaction 0-100% excess carbonylchloride (such as a dibromide or dichloride, i.e., phosgene) with the corresponding polyol, i.e., (HO)nR, in the presence or in the absence of tetraallylsilane (for example, tetramethylrhodamine) and in the presence or in the absence of solvent until the reaction is completed. Excess carbonylcyanide or phosgene is removed by steaming or by distillation. A non-limiting example of the impressive structures include 1,1,1-Tris(hydroxymethyl)ethane, 1,1,1-Tris(hydroxymethyl)propane, 1,1,1-Tris(hydroxymethyl)butane, glycerol, 1,2,3-trihydroxybenzene, 1,2,3-trihydroxybutane, 1,2,4-trihydroxybutane, 1,2,6-trihydroxybenzene, 1,3,5-trihydroxytoluene, pentaerythritol, 1,2,3,4-tetrahydroquinolin, 1,1,1,5,5,5-hexa(hydroxymethyl)-3-oxapentane, 1,1,1,5,5,9,9,9-Oct(hydroxymethyl)-3,7-dioxanonane and polycaprolactones and-tetraol structures F and G, respectively, and polyetherdiol and-tetraol structures J and K, respectively.

In accordance with another variant of new poly(monoperoxyphthalate) structure And can be obtained by interaction of tert-alkyl-peroxyacetate patterns L

< / BR>
(where X = Br or Cl)

with a polyol, i.e., (HO)nR, in the presence of an inorganic or organic base and optionally in the presence of one or more solvents. Tert-alkylbenzenesulfonate structure L can be obtained by interaction of tert-alkylhydroperoxide patterns In excessive carbonylchloride (carbonylcyanide or phosgene) and removal of excess carbonylchloride by Stripping or distillation.

Non-limiting examples of inorganic or organic bases, neobisiidae tert-alkylbenzosulphonate patterns, L include tert-butylperoxybenzoate, tert-nelproscarpharmacy, 2-methyl-2-interproximate, 3-methyl-3-pentyl-peroxyformic and 3-methyl-1-butyn-3-isproccallframe.

New peroxidation bis(monoperoxyphthalate) patterns And where R1selected from 1,1,4-trimethyl-4(tert-BUTYLPEROXY)-penciling radical and 1,1,4-trimethyl-4(tert-AMYLPEROXY)penciling radical and n = 2, can be obtained by interaction of a hydroperoxide selected from 1,1,4-trimethyl-4(tert-BUTYLPEROXY)intelligrated and 1,1,4-trimethyl-4(tert-AMYLPEROXY)intelligrated, with bis (halogenfree) structure (where n = 2) at a temperature of from -30 to 50oWith not necessarily in the presence of an inorganic or organic base and optionally in the presence of one or more solvents.

Non-limiting examples of suitable bis(halogen formate) structure C (where n = 2), which can be subjected to interaction with 1,1,4-trimethyl-4(tert-BUTYLPEROXY)IntelliProtector or 1,1,4-tri-methyl-4(tert-AMYLPEROXY)IntelliProtector include 1,2-bis(chlorocarbonyl)ethane, 1,2 and 1,3-bis(chlorocarbonyl) propane, 2,2-dimethyl-1,3-bis(chlorocarbonyl)propane, 1,6-bis(Locaboat) structures NN and II

< / BR>
< / BR>
The above bis(halogenfree) can be obtained by interaction 0-100% excess carbonylchloride (such as a dibromide or dichloride, i.e., phosgene) with the corresponding diola in the presence or in the absence of tetraallylsilane (for example, tetramethylrhodamine) and in the presence or in the absence of solvent until the reaction is completed. Excess carbonylcyanide or phosgene is removed by steaming or by distillation.

Non-limiting examples of suitable diols interacting with carbonylchloride with the formation of bis(halogenfree) structure (where n = 2) include 1,2-ethanediol, 1,2-and 1, 3-propandiol, 1,2-, 1,3-and 1,4-butanediol, 2-butene-1,4-diol, 2-ethyl-1,3 hexanediol, 2, 2, 4-trimethyl-1,3-pentanediol, 1,6-hexanediol, dietilen-glycol, dipropyleneglycol and polycaprolactone patterns JJ (diols TONE:

< / BR>
such as TONE200 and TONEH210, manufacturing Union Carbide Corporation) and polyalkyleneglycol patterns QC:

< / BR>
New poly(monoperoxyphthalate) patterns And Illustrative examples

Non-limiting examples of new poly(monoperoxyphthalate) patterns And addition compounds in the working examples include follow is)propane,

1,1,1-Tris(tert-anilinoquinazolines)butane,

1,1-bis[2-(tert-anilinoquinazoline)ethoxymethyl] -1-[2-(tert-butylperoxycyclohexyl)ethoxymethyl]propane,

1-[2-(tert-anilinoquinazoline)ethoxymethyl] -1,1-bis[2-(tert-butylperoxycyclohexyl)ethoxymethyl]propane

1,2,3-Tris(tert-anilinoquinazoline)propane, 1,2,3-Tris(tert-butylperoxycyclohexyl)hexane, 1,2,3-Tris(tert-butylperoxycyclohexyl)heptane, 1,2,4-Tris(tert-butylperoxycyclohexyl)butane, 1,2,6-Tris (tert - butylperoxycyclohexyl)hexane, 1,3,5-Tris(tert-butylperoxycyclohexyl)cyclohexane, tetrakis(tert-anilinoquinazolines)methane, 1,2,3,4-tetrakis(tert-anilinoquinazoline)butane, 1,1,1,5,5,5-hexa(tert-butylperoxyisopropyl)-3-oxapentane, 1,5-bis[1,1,4-trimethyl-4-(tert-AMYLPEROXY) antiperoxidative 3-3-oxapentane, 1,1,1-Tris[1,1,4-trimethyl-4(tert-BUTYLPEROXY)interprocesscommunication] propane, 1,1,1,5,5,9,9,9-Oct(tert-butylperoxybenzoate-methyl)-3,7-dioxanonane and Tris - and tetrakis(tert-alkylphenolethoxylate) polycaprolactone and-tetraols and polyetherdiols and-tetraols, i.e., compounds of structures M, N, O and P, respectively:

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< / BR>
< / BR>
where t-C5H11is the t 2-methyl-2-heptyl or 1,1,3,3-TETRAMETHYLBUTYL.

New poly(monopectinate) patterns And the Usefulness

A. Polymerization ethylenedeamine monomers

As was established in the processes of free-radical polymerization ethylenedeamine monomers at suitable temperatures and pressures new peroxide compounds structure And the present invention are effective agents in respect of profitability (lower needs in the initiator, and so on). Ethylenedeamine monomers include olefins such as ethylene, propylene, styrene, alpha-methylsterol, n-methylsterol, chloresterol, bracciali, vinylbenzoate, vinylpyridine and divinylbenzene; diolefin, such as 1,3-butadiene, isoprene and chloroprene; complex vinyl esters such as vinyl acetate, finalproject, vanillaware, vinylbenzoate and diphenylcarbonate; unsaturated NITRILES such as Acrylonitrile and Methacrylonitrile; acrylic and methacrylic acids and their anhydrides, esters and amides, such as the anhydride of acrylic acid, allyl-, methyl-, ethyl-, n-butyl, 2-hydroxyethyl, glycidyl-, lauryl -, and 2-ethylhexylacrylate and methacrylates and acrylamide and methacrylamide; maleic and itacademy anhydrides; maleic, taconova and fumaric acid and their esters; vinylsilane and vinylidenefluoride; perhalogenated, such as tetrafluoroethylene, HEXAFLUOROPROPYLENE and chlorotrifluoroethylene; simple vinyl esters, such as metilidinovy ether, ethylenically ether and n-butylvinyl ether; allyl complex esters, such as ZIOC scientists, allylbenzene, allegationsof, triethylphosphate, diallylphthalate, diallyl-fumarate, diallylphthalate, dellilachip, diallylmalonate, bis(allylcarbamate) diethylene glycol (i.e., ADC); acrolein; methyl vinyl ketone are, or mixtures thereof.

When free-radical polymerization grafting on the polymer ethylenedeamine monomers at suitable temperatures and pressures new peroxide compounds structure And are effective agents in relation to the effectiveness of vaccinations. Ethylenedeamine monomers include styrene monomers such as styrene, alpha-methylsterol, n-methylsterol, chloresterol, bracciali and vinylbenzoate; unsaturated NITRILES such as Acrylonitrile and Methacrylonitrile; esters of acrylic and methacrylic acids, such as allyl-, methyl-, ethyl-, n-butyl, 2-hydroxyethyl-, glycidyl, laureli 2-ethylhexylacrylate and methacrylates; and maleic anhydride. Grafted polymers include polybutadiene and polyisoprene. Two important the polimerov, include high impact polystyrene (HIPS) and Acrylonitrile-butadiene-styrene (ABS, ABS). HIPS are obtained by free-radical grafting styrene on polybutadiene, and ABS are obtained by free-radical grafting Acrylonitrile and styrene on polybutadiene. Such polybutadiene-modified compounds have a higher impact strength than the unmodified polymers.

In the traditional processes of polymerization and copolymerization ethylenedeamine monomers and grafting ethylenedeamine monomers in the main chain of the polymers commonly used temperature in the range from 0 to 190oC, preferably from 20 to 175oS, and more preferably from 30 to 160oWith, and the content of poly(monoperoxyphthalate) patterns And (in pure form) from 0.002 to 10% or more, preferably 0.005 to 2%, and more preferably from 0.01 to 1% by weight of monomer. New peroxides of the present invention can be used in combination with other initiators of free-radical polymerization, such as 1,5-di(tert-butylperoxycyclohexyl)-3-oxapentane, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(isopropoxycarbonyl)hexane, 2,5-dimethyl-2-(2-ethylhexanoylperoxy)-5-(trattorie of those listed at the bottom of the column 4 and the top of the columns 5 description of the U.S. patent 4525308 (issued by Pennwalt Corporation June 25, 1985). The use of peroxide compounds of the present invention in combination with the abovementioned initiators adds flexibility to the processes used by manufacturers of polymers, and allows them to implement "thin debug polymerization processes.

C. Curing unsaturated polyesters

During curing of unsaturated polyester resins by heating at suitable curing temperatures in the presence of free-radical curing agents new poly(monoperoxyphthalate) structure And the present invention exhibit enhanced curing activity in the curing of unsaturated complex polyesters. Unsaturated polyester resins that can be solidified new poly(monoperoxyphthalate) according to the present invention usually contain unsaturated complex polyester and one or more Ethylenediamine monomers.

Unsaturated polyesters are, for example, polyesters obtained by esterification of at least one ethylenedeamine di - or higher polycarboxylic acid (or anhydride or Gal the slot, musicanova acid, Tarakanova acid, allylmalonate acid, tetrahydrophtalic acid and other saturated and unsaturated di - or higher polyols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-and 1,3-propandiol, 1,2-, 1,3 - and 1,4-butanediol, 2,2-dimethyl-1,3-propandiol, 2-hydroxymethyl-2-methyl-1,3-propandiol, 2-butene-1,4-diol, 2-butyn-1,4-diol, 2,4,4-trimethyl-1,3-pentanediol, glycerin, pentaerythritol, mannitol and others. You can also use a mixture of such di - and higher PolicyKit and/or a mixture of such di - or higher polyols. Ethylenediamine di - or higher polycarboxylic acids may be partially replaced by a saturated di - or polycarboxylic acids such as adipic acid, succinic acid, sabotinova acid and others, and/or aromatic di - or higher polycarboxylic acids such as phthalic acid, trimellitate acid, pyromellitate acid, isophthalic acid and terephthalic acid. Used acid may have a substitutional group such as halogen. Examples of suitable halogen-substituted acids are, for example, tetrachlorophthalic acid, tetrabromophthalic acid, 5,6-dicarboxy-1,2,3,4,7,7-hexachlorobicyclo(2,2,1)-2-hepten and others.

Other types of unsaturated polyester resins can be solidified using the new peroxide compounds according to the present invention as a curing catalyst. These resins are called unsaturated polymers of vinyl esters, consist of vinylester resin and one or more are able to polymerization of the Monomeric components. Vinylester polymer component can be obtained by osushestvleniya bisphenol a (i.e. 2,2-(4-hydroxyphenyl)propane), in the presence of a base such as sodium hydroxide, to obtain a condensation product having end epoxypropyl produced from chlorapatite. The subsequent interaction of the product of condensation polymerized with unsaturated carboxylic acids such as acrylic and methacrylic acid, in the presence or in the absence of acidic or basic catalysts leads to the formation of vinyl ester polymer component. To complete the receipt of the unsaturated polymer vinyl esters usually added styrene in the quality of the polymerized Monomeric component.

Usually use a temperature in the range of about from 20 to 200oWith and content of the new poly(monoperoxyphthalate) patterns And from about 0.05 to 5%, or more preferably from 0.10 to 4%, and more preferably from 0.25 to 3% by weight of curable unsaturated polyester resin.

The above unsaturated polyester resin can be filled with various materials, such as sulfur, glass, carbon and boron fibers, carbon black, silicas, silicates, metals, clays, carbonates, metals, antioxidants (AO), stabilizers against the action of heat, the ult is, the AK zinc oxide, porophores, nucleating and others.

C. Curing allylchloroformate (ADC ADC) resins

During curing or polymerization of bis(allylcarbamate) diethylene glycol (ADC)

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by heating the ADC monomer under suitable curing temperatures in the presence of free-radical curing agents new poly(monoperoxyphthalate) structure And the present invention exhibit enhanced curing or polymerized activity in relation to ADC-monomers. Industrial production ADC performs Pittsburgh Plate Glass Company (PPG) monomer CR-39 (CAS per. N 142-22-3), which is produced by the interaction of bis(chloroformate) of diethylene glycol with allyl alcohol in the presence of alkali (R. Dowbenco, Izdat. J. I. Kroschwitz and M. Howe-Grant, Kirk-Othmer Encyclopedia of Chemical Technology, "Allyl Monomers and Polymers", fourth edition, volume 2, Willey-Interscience Publication, John Willey & Sons, Inc., New York, 1992, S. 163-168). ADC-monomer can be overiden or polymerized alone or with other comonomers, such as esters of acrylic acid, esters of methacrylic acid, allyl complex esters, validatability (for example, di-alilttle), maleic anhydride and other monomers, to obtain setprimarykey ADC-monomers is carried out in mass (without solvent). Typically, the curing or polymerization of the ADC monomers for forming cast sheets or lenses is carried out in two stages. The first stage comprises the bulk of the polymerization and is carried out in the presence of a curing initiator at a temperature of from 35 to 150oC. the Time of curing or polymerization of the first stage ranges from about 5 to 50 hours Second stage of the curing or polymerization of the ADC-monomers include dauvergne or annealing ADC-resin for one or more hours at 100-170oC.

New poly(monoperoxyphthalate) patterns And are usually used in amounts of about 1 to 6% or more, preferably 2-5%, more preferably 2.5 to 4% by weight of the cured or polymerized ADC monomer.

The above-described ADC-resin can be filled with various materials, such as antioxidants (AO), stabilizers against the action of heat, ultraviolet radiation (UV) light and tonal pigments, photochromic additives and dyes. In addition, the ADC-resin may contain additives such as acrylic polymers and antishrink low molecular weight acrylic resins disclosed in U.S. patent 4217433 (issued Pecnnwalt Corporation August 12, 1980 ). Such antishrink additives IP is Estamirov and crosslinking thermoplastic polymers

During curing elastomeric compounds and cross-linking of polymer compounds by heating at suitable curing temperatures and crosslinking in the presence of free-radical curing and cross-linking agents new poly(monoperoxyphthalate) structure And the present invention are curing and cross-linking activity.

Elastomeric resins which can be solidified using the new poly(monoperoxyphthalate) of the present invention include elastomers such as ethylene-propylene copolymers (EPR), ethylene-propylene-diene terpolymer (EPDM), polybutadiene (PBD), silicon rubber (SR), nitrile rubber (NR), neoprene, forecaster and ethylene-vinyl acetate copolymer (EVA).

Polymer compounds that can be stitched new poly(monoperoxyphthalate) of the present invention include olefinic thermoplastics, such as chlorinated polyethylene (CPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE). Other stitched thermoplastic polymers include polyvinyl chloride (PVC), polystyrene, poly(vinyl acetate), polyacrylates, polyesters, polycarbonates, etc.

Usually the s) from about 0.1 to 10%, preferably from 0.5 to 5%, and more preferably from 0.5 to 3% by weight of curable elastomeric resin or stitched olefin polymer.

Curable elastomeric resin or stitched polymer can be, though not necessarily, filled with the materials listed above for use with conventional unsaturated complex polyesters.

E. Modification of polyolefins and other polymers

In the processes of modification of polyolefins (e.g., favorable degradation of polypropylene (PP) by reducing the molecular weight of the polymer and reduce the molecular mass distribution of PP and improvement of molecular mass and film-forming properties of linear low density polyethylene (LLDPE)), and copolymers of new poly(monoperoxyphthalate) structure And the present invention are modifying in relation to the polyolefin activity. Other polymers that can be modified Tris - and poly(monoperoxyphthalate) include high density polyethylene (HDPE), ethylene-propylene copolymer, etc.

Usually use a temperature in the range of about from 140 to 340oAnd the content of poly(monoperoxyphthalate) approximately from 0.001 to 1.0%, prepost. the quality of socializaton modification is possible, although not necessarily, the use of molecular oxygen in an amount up to 1% by mass.

New poly(monoperoxyphthalate) patterns And Examples of obtaining and useful

The following additional examples illustrate the best ways of implementing the present invention and are presented for detailed descriptions of the methods of obtaining and usefulness of the proposed compounds and should not be considered as limiting the scope of invention.

Example 1. Obtain 1,1,1-Tris(tert-butylperoxycyclohexyl)ethane (I-1)

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In this example, the product was obtained in two stages of synthesis. In the first stage, 1,1,1-Tris(hydroxymethyl)ethane (0.15 mol) was subjected to interaction with excess phosgene (0.85 mol) in 175 ml of 1,4-dioxane with 0-8oC. To suppress the formation of cyclic carbonate was added 1,1,3,3-tetramethylrhodamine (0.4 g). Upon completion of the reaction, excess phosgene and solvent drove away from the product at 15-30oC and reduced pressure to obtain 1,1,1-Tris(chlorocarbonylsulfenyl)ethane in the liquid content of the product according to the analysis of 89.3 per cent and the adjusted output 74,6%.

In the second stage, 1,1,1-Tris(chlorocarbon is rockside potassium and surface-active substances and as a result received the product, as described below:

In a reactor with a capacity of 300 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded 70,0 g (0.25 mol) of 20% aqueous solution of potassium hydroxide, 25 g (0.25 mol) 90,2% tert-butylhydroperoxide and 10 drops of TERGITOLNP-10 [a mixture of surface-active substances containing poly(oxy-1,2-ethandiyl), -(4-nonylphenyl)--hydroxy-; 26027-38-3 in the CAS register, and poly (oxy-1,2-ethandiyl), -hydro--hydroxy-; 25322-68-3 in the CAS register; production Union Carbide], and the resulting solution was stirred at 25oC for 10 minutes To the stirred mixture at 22-29oWith slowly rose to 17.2 g (0.05 mol) 89,3% 1,1,1-Tris(chlorocarbonylsulfenyl)ethane within 25 minutes after the addition, the reaction mass was stirred 3 h at 30-35oWith, after which was added 150 ml of MTBE (methyl tert-butyl ether) and the reaction mass was stirred for one minute at 30-35oC. Then the lower aqueous layer was separated, and the organic layer was cooled to 17oC and washed with 100 ml of 10% aqueous solution of potassium hydroxide. Then the organic layer was washed three times with 50 ml portions of 10% aqueous Hydrosulphite solution of sodium, and then 100 ml of 10% aqueous sodium hydroxide solution and then with saturated aqueous solution of sulfate nattel, was removed in vacuum, the solvent with the receipt of the balance of 7.4 g (31,6% theoretically, without amendments) of a white solid substance, so pl. = 55-60oC. Infrared (IR) spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1790 cm-1and the main carbonyl band carbonate at about 1755 cm-1. The IR spectrum no absorption bands hydroxide (HE). The product contained 9,42% active oxygen(theoretically of 10.25%) according paroxetina method of determining the content of active oxygen, therefore, the product analysis was 91,9%, and the adjusted output 29,1%.

According to the production method, data output and data, IR spectrum, the product obtained by this reaction was specified in the header of the target product.

Example 2. Obtain 1,1,1-Tris(tert-butylperoxycyclohexyl)propane (I-2)

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In this example, the product was obtained in two stages of synthesis. In the first stage, 1,1,1-Tris(hydroxymethyl)propane (0.10 mol) was subjected to interaction with excess phosgene (of 0.60 mol) in 200 ml of 1,4-dioxane at 2-8oC. To suppress the formation of cyclic carbonate was added 1,1,3,3-tetramethylrhodamine (0.3 g). After re who eat 1,1,1-Tris(chlorocarbonylsulfenyl) propane in liquid form containing product according to the results of the analysis 87.7%) and adjusted the output is 95.6%.

In the second stage, 1,1,1-Tris(chlorocarbonylsulfenyl)propane was subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide and a surfactant, and the resulting product was received as described below:

In a reactor with a capacity of 300 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded 56,0 g (0.20 mol) of a 20% aqueous potassium hydroxide and 19.5 g (0.20 mol) of 92% tert-butylhydroperoxide, and the resulting solution was stirred at approximately 25oC. To the stirred mixture at 23-31oWith was slowly added a solution of 18.3 g (0.05 mol) 87,7% 1,1,1-Tris(chlorocarbonylsulfenyl)propane and 50 ml of MTBE within 30 minutes after the addition, the reaction mass was stirred 3 h at 30-32oWith, after which was added 50 ml of MTBE and the reaction mass was stirred for one minute at 30-32oC. Then the lower aqueous layer was separated, and the organic layer was cooled to 12oC and washed with 50 ml of 10% aqueous Hydrosulphite solution of sodium. Then the obtained organic layer was washed twice with 50 ml portions of 3% aqueous solution of sodium bicarbonate. The product solution was dried over 5% by weight anhydrous gS04and by filtering exhaust Noah colorless liquid. The IR spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1792 cm-1and the main carbonyl band carbonate at about 1767 cm-1. The IR spectrum was only a trace of absorption bands HE. The product contained 8,65% active oxygen (theoretically 9,95%) according paroxetina method of determining the content of active oxygen, therefore, the product analysis was 86.9 per cent, and the corrected yield was 38.9%.

According to the production method, data output and data, IR spectrum, the product obtained by this reaction was specified in the header of the target product.

Example 3. Getting polycaprolacton-Tris(mono-tert-butylperoxybenzoate) (I-3)

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where the sum of x, y and z is equal to about 2 and R3is triradical.

In this example, the product was obtained in two stages of synthesis. In the first stage of 0.12 mol of polycaprolactone (s-1) (TONE 0301; molecular weight = 300; production Union Cabride Corp.):

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where the sum of x, y and z is equal to about 2 and R3is triradical were subjected to interaction with excess phosgene (of 0.60 mol) at 5-10oC. Upon completion of the reaction, excess phosgene drove away from the product when the 15th of the liquid content of the product according to the results of the analysis 91,0% and the corrected yield of 84.2 per cent.

In the second stage polycaprolacton-Tris(chloroformate) were subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide, and the product was received as described below:

In a reactor with a capacity of 250 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded 28,0 g (0.10 mol) of a 20% aqueous potassium hydroxide, and 12.9 g (0.10 mol) of aqueous 70% tert-butylhydroperoxide and 3 drops (approximately 0.1 g) TERGITOL NP-10 at 20-30oC. the resulting solution was stirred at approximately 25oC. To the mixed solution at 23-29oWith was slowly added to 16.1 g (0.03 mol) 91,0% polycaprolacton-Tris(chloroformate) for 20 minutes To ensure good mixing was added about 50 ml of MTBE. Upon completion of addition, the reaction mass was stirred 3 hours at 30oWith, even while adding MTBE (50-60 ml). Then the reaction mass was allowed to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic layer was cooled to 15oC and washed with 50 ml of 10% aqueous Hydrosulphite solution of sodium, and then washed with 50 ml of 10% aqueous potassium hydroxide solution and 50 ml portions of a saturated aqueous solution solarbattery drier, was removed in vacuum, the solvent is getting in the remainder of 19.6 g (approximately 100% theoretically, without amendments) as a colourless liquid. The IR spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1785 cm-1and the main carbonyl band carbonate or ether complex at about 1740 cm-1. The IR spectrum no absorption band HE. The product contained 6,69% active oxygen (theoretically 7,40%) according paroxetina method of determining the content of active oxygen, therefore the content of the product according to the results of the analysis were $ 90.4%, and the adjusted output was 91.3 percent.

Example 4. Getting polycaprolacton-Tris(mono-tert-butylperoxybenzoate) (I-4)

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where the sum of x, y and z is equal to about 4 and R3is triradical.

In this example, the product was obtained in two stages of synthesis. In the first stage of 0.05 mol of polycaprolactone (p-2) (TONE 0305; molecular weight = 540; production Union Carbide Corp.)

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where the sum of x, y and z is equal to about 4 and R3is triradical were subjected to interaction with excess phosgene (0.45 mol) at 3-7oC. Upon completion of the reaction, excess phosgene drove away from the product at 15-25oAnd ponie the product analysis is 97.9% and the corrected yield of 93.3%.

In the second stage polycaprolacton-Tris(chloroformate) were subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide, and the product was received as described below.

In a reactor with a capacity of 200 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded 15.7 g (0.07 mol) of 25% aqueous solution of potassium hydroxide and 9.0 g (0.07 mol) of 70% aqueous tert-butylhydroperoxide. The resulting solution was stirred at approximately 25oC. To the mixed solution at 24-28oWith slowly added 14.8 g (0.02 mol) 97,9% polycaprolacton-Tris(chloroformate) within 15 minutes after the addition, the reaction mass was stirred for 3.5 h at 28-32oWith, after which was added 80 ml of MTBE, and the reaction mass was stirred for one minute at 28-32oC and then allowed to separate. Then the lower aqueous layer was separated and the remaining organic layer was cooled to 15oC and washed with 25 ml of 10% aqueous Hydrosulphite solution of sodium. Then the obtained organic layer is washed with 25 ml of 10% aqueous potassium hydroxide solution and 50 ml portions of a saturated aqueous solution of sodium sulfate to obtain a pH of 7-8. The product solution was dried by receipt of the balance of 17.4 g (98% of theoretically without amendments) as a colourless liquid. The IR spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1785 cm-1and the main carbonyl band carbonate or ether complex at about 1730 cm-1. The IR spectrum was only a trace of absorption bands HE. The product contained 5,00% active oxygen (theoretically of 5.40%) according paroxetina method of determining the content of active oxygen, therefore, the product analysis was 92,6% and the corrected yield was 90.7 percent.

According to the production method, data output and data, IR spectrum, the product obtained by this reaction was specified in the header of the target product.

Example 5. Obtain 1,1,1-Tris[2-(tert-butylperoxycyclohexyl)ethoxymethyl]propane (I-5)

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In this example, the product (i.e., 1,1,1-Tris[2-(tert-butylperoxycyclohexyl)ethoxymethyl] propane I-5) was obtained in two stages of synthesis. In the first stage of 0.15 mol simple polyetherdiol (i.e., 1,1,1-Tris[2-(hydroxyethoxymethyl] propane, p-3 (commercial triology product VORANOL 234-630; molecular weight = 267; manufacture of Dow Chemical)

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were subjected to interaction with excess phosgene (of 0.65 mol) at 3-7oC. Then reacts Shen drove away from the product at 20-25oC and reduced pressure for 5 hours to obtain polyester-Tris (chloroformate) in the form of a transparent viscous liquid containing product according to the analysis of 97.4% and the corrected yield of 94.8%.

In the second stage, the polyester-Tris(chloroformate) were subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide, and the product was received as described below:

In a reactor with a capacity of 200 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded to 29.4 g (0,105 mol) of a 20% aqueous potassium hydroxide, 13.5 g (0,105 mol) of aqueous 70% tert-butylhydroperoxide and 3 drops (approximately 0.1 g) TERGITOL NP-10 at 20-30oC. the resulting solution was stirred at approximately 25oC. To the mixed solution at 23-29oWith was slowly added a solution consisting of 14.0 g (0.03 mol) of 97.4% polyester-Tris(chloroformate) and 20 ml of MTBE within 15 minutes after the addition, the reaction mass was stirred for 2.5 h at 30oWith, after which was added 80-90 ml of MTBE, and the reaction mass was stirred for one minute at 30oC and then allowed to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic with the thief was then washed with 50 ml of 10% aqueous Hydrosulphite solution of sodium. The obtained organic layer is then washed with 50 ml saturated aqueous solution of potassium bicarbonate. Next, the organic layer was washed with 50 ml of a saturated aqueous solution of sodium sulfate to obtain a pH of approximately 7. The product solution was dried over 5% by weight anhydrous MgSO4and by filtering the spent desiccant was removed in vacuum, the solvent is getting in the remainder of 18.3 g (approximately 100% theoretically, without amendments) colorless liquid product. The IR spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1785 cm-1and the main absorption band of carbonate at about 1735 cm-1. The IR spectrum no absorption band HE. The product contained 7,52% active oxygen (theoretically 7,81%) according paroxetina method of determining the content of active oxygen, therefore, the product analysis was 94,2%, and the adjusted output was 93,7%.

According to the production method, data output and data IR spectrum of the product obtained in this reaction was specified in the header of the target product.

Example 6. Getting polycaprolacton-tetrakis(mono-tert-butylperoxybenzoate) (I-6)

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where is Lee two-stage synthesis. In the first stage of 0.03 mol polycaprolactone (p-4) (experimental caprolactone oligomeric tetraol TONE 4411; molecular weight = 1006; production Union Carbide Corp.)

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where the sum of v, x, y and z is equal to about 8 and R6is tetradecyl were subjected to interaction with excess phosgene (0.35 mol) at 3-7oC. the Reaction mixture was then stirred 5 h at 10-20oWith and gave it to precipitate overnight at 20-25oC. Then the excess phosgene drove away from the product at 20-25oC and reduced pressure for 5 hours to obtain polycaprolacton-tetrakis(chloroformate) in the form of a transparent viscous liquid containing product according to the analysis of 97.3% and a corrected output 91,9%.

In the second stage polycaprolacton-tetrakis(charformat) were subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide, and the product was received as described below:

In a reactor with a capacity of 200 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded 11.2 g (0.05 mol) of 25% aqueous potassium hydroxide solution and 6.4 g (0.05 mol) of aqueous 70% tert-butylhydroperoxide at 20-30oC. Obtained rasor, consisting of 12.9 g (0.01 mol) of 97.3% polycaprolacton-tetrakis(chloroformate) and 30 ml of MTBE within 15 minutes after the addition, the reaction mass was stirred 3 h at 30-35oWith, after which was added 70 ml of MTBE, and the reaction mass was stirred for one minute at 30-35oAnd then gave it to split. Then the lower aqueous layer was separated, and the organic layer was cooled to 15oC and washed with 50 ml of 10% aqueous solution of potassium hydroxide. Then the crude product solution was washed with 50 ml of 10% aqueous Hydrosulphite solution of sodium. Next, the resulting organic layer was washed with 10% aqueous solution of potassium bicarbonate to obtain a pH of approximately 7. The resulting solution was dried over 5% by weight anhydrous gSO4and by filtering the spent desiccant was removed in vacuum, the solvent with the receipt of the balance of 14.9 g (approximately 100% theoretically, without amendments) of a viscous colorless liquid. The IR spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1785 cm-1and the main carbonyl band carbonate or ether complex at about 1730 cm-1. The IR spectrum no absorption band HE. The product consisted of 3.73% active oxygen (theoretically 4,35%) according to peltatum analysis was 85,7%, and the adjusted output was 86.9 per cent.

According to the production method, data output and data, IR spectrum, the product obtained by this reaction was specified in the header of the target product.

Example 7. Obtaining a polyester-tetrakis(mono-tert-butylperoxybenzoate) (I-7)

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where the sum of q, r, s and t is equal to about 6-7.

In this example, the product was obtained in two stages of synthesis. In the first stage of 0.075 mol poliferation (p-5) (PLURACOL PEP 550; molecular weight = 500; production BASF Corporation)

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where the sum of q, r, s and t is equal to about 6-7 were subjected to interaction with excess phosgene (of 0.60 mol) at 3-7oC. Then the reaction mixture was stirred for 2-3 h at 1-20oWith and gave it to precipitate overnight at 20-25oC. Then the excess phosgene drove away from the product at 20-30oC and reduced pressure to obtain a polyester-tetrakis(chloroformate) in the form of a transparent liquid content of the product according to the analysis of 100% and the corrected yield of 97.4%.

In the second stage, the polyester-tetrakis(charformat) were subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide and the product was received as described below.

ronkay, download 29,2 (0.13 mol) of 25% aqueous potassium hydroxide solution and 16.7 g (0.13 mol) of 70% aqueous tert-butylhydroperoxide when 22-29oC. the resulting solution was stirred at approximately 25oC. To the mixed solution at 23-28oWith was slowly added to 18.8 g (0,025 mol) 100% polyester-tetrakis(chloroformate) within 15 minutes after the addition, the reaction mass was stirred 3 h at 25-30oWith, after which was added 100 ml of MTBE, and the reaction mass was stirred for one minute at about 30oC and then allowed to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic layer was cooled to 12oC and washed with 50 ml of 10% aqueous Hydrosulphite solution of sodium, and then 50 ml of 10% aqueous potassium hydroxide solution and 50 ml portions of a saturated aqueous solution of sodium sulfate to obtain a pH of 7-8. The product solution was dried over 5% by weight anhydrous gSO4and by filtering the spent desiccant was removed in vacuum, the solvent is getting in the remainder of 22.4 g (92.9% of theoretically, without amendments) as a colourless liquid. The IR spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1785 cm-1and the main carbonyl band carbonate or Kononova oxygen (theoretically 6,64%) according paroxetina method of determining the content of active oxygen, therefore, the product analysis was 92,8%, and the adjusted output amounted to 86.3%.

According to the production method, data output and data, IR spectrum, the product obtained by this reaction was specified in the header of the target product.

Example 8. Getting polycaprolacton-bis(mono-tert-butylperoxybenzoate) (A-1)

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where the sum of x and y is equal to about 4 and R2is biradical.

In this example, the product was obtained in two stages of synthesis. In the first stage of 0.03 mol polycaprolactone (C-6) (diol TONE0200; molecular weight = 530; production Union Carbide Corp.)

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where the sum of x and y is equal to about 4 and R3is biradical were subjected to interaction with excess phosgene in accordance with the above described process. The result has been polycaprolacton-bis(chloroformate) in the form of a pink viscous liquid containing product according to the analysis of 100%.

In the second stage polycaprolacton-bis(chloroformate) were subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide and the product was received as described below:

In a reactor with a capacity of 400 ml with water one solution of potassium hydroxide, 10.0 g of water and 14.1 g (0.11 mol) of aqueous 70% tert-butylhydroperoxide at 20-30oC. the resulting solution was stirred at approximately 25oC. To the mixed solution at 23-31oWith slowly rose to 32.7 g (0.05 mol) 100% polycaprolacton-bis(chloroformate) within 25 minutes after the addition was added 75 ml of MTBE, and the reaction mass was stirred for about 2 h at 302oWith, after which was added 125 ml of MTBE, and the reaction mass was stirred for one minute at 30oC and then allowed to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic layer was cooled to 15oC and washed with 50 ml of 10% aqueous Hydrosulphite solution of sodium at 15-25oC. dividing the mass into two liquid phases was very slow. The addition of sodium sulfite accelerated separation. The lower aqueous phase was separated and poured. After that, the upper organic solution was washed twice with 50 ml portions of 20% aqueous potassium hydroxide solution at 20-30oC. the resulting organic layer was then washed with a saturated aqueous solution of sodium sulfate to obtain a pH of approximately 7. Organic product solution was dried over 5% by weight anhydrous MgS04and, filtering otrb is, the ez amendments) of a viscous colorless liquid. The IR spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1785 cm-1and the main carbonyl band carbonate or ether complex at about 1731 cm-1. The IR spectrum no absorption band HE. The product contained 3,97% active oxygen (theoretically 4,20%) according paroxetina method of determining the content of active oxygen, therefore the content of the product according to the results of the analysis made 94.5%, and the adjusted output was 84,1%.

According to the production method, data output and data, IR spectrum, the product obtained by this reaction was specified in the header of the target product.

Example 9. Obtain 1,1,1-Tris[2-(tert-AMYLPEROXY-carbonyloxy)ethoxymethyl]propane (I-8)

< / BR>
In this example, the product (i.e., 1,1,1-Tris[2-(tert-anilinoquinazoline)ethoxymethyl] propane I-8) was obtained by interaction polyester-Tris(chloroformate) of VORANOL 234-630 (example 5), tert-AMYLPEROXY and an aqueous solution of potassium hydroxide as described below:

In a reactor with a capacity of 200 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded 1 is correctly 0.1 g) TERGITOL NP-10 at about 20-25oC. the resulting solution was stirred at a temperature of 25oC. To the mixed solution at 24-32oWith slowly was added 9.3 g (at 0.020 mol) 98,7% polyester-Tris(chloroformate) (VORANOL 234-630) for 15 minutes During the addition was added 50 ml of MTBE. Then the reaction mass was stirred 3.0 hours at about 30oC. At the end of the period of reaction was added to 50 ml of MTBE and the reaction mass was stirred for two minutes and then gave it to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic layer was cooled to 20oC and washed with 50 ml of 20% aqueous solution of potassium hydroxide. The crude product solution was then washed with 50 ml of 15% aqueous Hydrosulphite solution of sodium. The obtained organic layer was then washed with saturated aqueous sodium hydrogen carbonate solution to obtain a pH of approximately 7. The product solution was dried over 5% by weight anhydrous gS04and by filtering the spent desiccant was removed in vacuum, the solvent with the receipt of the balance of 10.8 g (approximately 82.2% of theoretically, without amendments) colorless liquid product. The IR spectrum of the product contained the main absorption band of the carbonyl monoperoxyphthalate at 1785 cm-1and the main strip of the active oxygen (theoretically 7,31%) according paroxetina method of determining the content of active oxygen, therefore, the content of the product according to the results of the analysis were $ 79.9%, and the adjusted output amounted to 65.7%.

According to the production method, data output and data, IR spectrum, the product obtained by this reaction was specified in the header of the target product.

Example 10. Obtaining a polyester-tetrakis(mono-tert-anilinoquinazoline) (I-9)

< / BR>
(where the sum of q, r, s and t is equal to approximately 6-7).

In this example, the product was obtained in two stages of synthesis. In the first stage poliferation (p-5) (PLURACOL PEP 550) were subjected to interaction with excess phosgene, resulting in polyester-tetrakis(chloroformate) of example 7.

In the second stage, the polyester-tetrakis(charformat) were subjected to interaction with tert-AMYLPEROXY in the presence of an aqueous solution of potassium hydroxide, and the product was received as described below:

In a reactor with a capacity of 250 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded 28,1 (0.10 mol) of a 20% aqueous potassium hydroxide, to 10.1 g (0.09 mol) of 92.6% tert-AMYLPEROXY and 2 drops (approximately 0.1 g) ALIQUAT336 (tricaprylmethyammonimum), production of Henkel Corporation), and obtained ,2 g (at 0.020 mol) 100% polyester-tetrakis(chloroformate) for 10 minutes Upon completion of addition, the reaction mass was stirred 5 h at about 35-40oWith, after which there was added 75 ml of MTBE, and the reaction mass was cooled to 25oC, stirred for one minute and then gave it to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic layer was washed with 50 ml of 20% aqueous potassium hydroxide solution and then 50 g of an aqueous solution of sodium sulfite with buffer properties (prepared by dissolving 1.2 g of acetic acid, 2.5 g of sodium acetate and 4.3 g of sodium sulfite in 42,0 g of water). The aqueous layer was poured, and the organic layer was washed with 100 g of saturated solution of sodium chloride. The product solution was dried over 5% by weight anhydrous MgSO4and by filtering the spent desiccant was removed in vacuum, the solvent with the receipt of the balance of 18.0 g (88,2% theoretically, without amendments) as a colourless liquid. The product contained 5,56% active oxygen (theoretically 6,27%) according paroxetina method of determining the content of active oxygen, therefore, the content analysis was to 88.7% and the corrected yield was 80,0%.

According to the method of obtaining and data output, the product obtained by this reaction was indicated is rbonate), I-10, PLURACOLTR-740

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where the sum of g, s and t is equal to about 6-7.

In this example, the product was obtained in two stages of synthesis. In the first stage, 0.06 mol polyetherdiol (C-7) (PLURACOL TP-740; molecular weight = 730, production BASF Corporation)

< / BR>
where the sum of r, s and t is equal to about 10-11 were subjected to interaction with excess phosgene (0.28 mol) at 3-7oC. Then the reaction mixture was stirred for 2-3 h at 10-20oWith and gave it to precipitate overnight at 20-25oC. Then the excess phosgene drove away from the product at 20-30oC and reduced pressure to obtain a polyester-Tris(chloroformate) And in the form of a transparent liquid content of the product according to the analysis of 100% and a corrected output 93,8%.

In the second stage, the polyester-Tris(chloroformate) And were subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide and the product was received as described below:

In a reactor with a capacity of 250 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded, and 19.6 g (0.07 mol) of 25% aqueous solution of potassium hydroxide and 9.0 g (0.07 mol) of 70% aqueous tert-butylhydroperoxide when 22-29oC. the resulting Rastaman) 100% polyester-Tris (chloroformate) And within 15 minutes Upon completion of addition, the reaction mass was stirred for 1.5 hours at 40oWith, after which there was added 17 g of ethylbenzene (EB), and the reaction mass was stirred for two minutes at about 30oC and then allowed to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic layer was cooled to 25oC and washed with 50 ml of 20% aqueous solution of hydroxide potassium, and then 50 g of an aqueous solution of sodium sulfite with buffer properties (prepared by dissolving 1.2 g of acetic acid, 2.5 g of sodium acetate and 4.3 g of sodium sulfite in 42,0 g of water and 50 g of a saturated solution of sodium chloride. The product solution was dried over 1.7 g of anhydrous gSO4and by filtering the spent desiccant, got 35,7 g of colorless liquid. The product solution contained 2,49% active oxygen (theoretically 4,45%) according paroxetina method of determining the content of active oxygen, therefore, the product analysis was 55.9 percent, and the adjusted output amounted to 92.4%.

According to the method of obtaining and data output, the product obtained by this reaction was specified in the header of the desired product in the form of 55.9% solution in ethylbenzene.

Example 12. Received avn about 10-11.

In this example, the product was obtained in two stages of synthesis. In the first stage of 0.05 mol of polyetherdiol (C-8) (PLURACOL GP-730; molecular weight = 730, production BASF Corporation)

< / BR>
where the sum of r, s and t is equal to about 10-11 were subjected to interaction with excess phosgene (0.40 mol) at 3-7oC. Then the reaction mixture was stirred for 2-3 h at 10-20oWith and gave it to precipitate overnight at 20-25oC. Then the excess phosgene drove away from the product at 20-30oC and reduced pressure to obtain a polyester-Tris(chloroformate) In the form of a transparent liquid content of the product according to the analysis of 100% and a corrected output 96,3%.

In the second stage, the polyester-Tris(chloroformate) were subjected to interaction with tert-butylhydroperoxide in the presence of an aqueous solution of potassium hydroxide and the product was received as described below:

In a reactor with a capacity of 250 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded 19,6 (0.07 mol) of 25% aqueous solution of potassium hydroxide and 9.0 g (,07 mol) of 70% aqueous tert-butylhydroperoxide when 22-29oC. the resulting solution was stirred at approximately 25oC. To the mixed solution at 23-28oWith medlenno mass was stirred 3 h at 25-30oWith, after which was added 100 ml of MTBE, and the reaction mass was stirred for one minute at about 30oC and then allowed to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic layer was cooled to 12oC and washed with 50 ml of 10% aqueous Hydrosulphite solution of sodium, and then 50 ml of 10% aqueous potassium hydroxide solution and 50 ml portions of a saturated aqueous solution of sodium sulfate to obtain a pH of 7-8. The product solution was dried over 5% by weight anhydrous gS04and by filtering the spent desiccant received in the remainder of 20.3 g (94% theoretically, without amendments) as a colourless liquid. The product contained 4.23% of active oxygen (theoretically 4,45%) according paroxetina method of determining the content of active oxygen, therefore, the product analysis was 95,1% and the corrected yield was 89.3 per cent.

According to the method of obtaining data and output the product obtained by this reaction was specified in the header of the target product.

Example 13. Obtain 1,5-bis(1,1,4-trimethyl-4-(tert-BUTYLPEROXY)antiperoxidase)-3-oxapentane, I-12

< / BR>
In this example, the product was obtained by the implementation of the mandate to engage (S-10)

< / BR>
and aqueous potassium hydroxide to obtain the product as described below:

In a reactor with a capacity of 250 ml with water jacket, equipped with a mechanical stirrer, thermometer and addition funnel, was loaded with 8.0 (0.05 mol) of 25% aqueous sodium hydroxide solution and 11.0 g (0,043 mol) of 91% 1,1,4-trimethyl-4-(tert-BUTYLPEROXY)intelligrated when 22-29oC. the resulting solution was stirred at approximately 25oC. To the mixed solution at 23-28oWith slowly was added 5.8 g (0,025 mol) of 99% diethylene glycol-bis(chloroformate) (C-9) within 15 minutes after the addition, the reaction mass was stirred for 3.5 hours at 30-35oWith, after which was added 50 ml of MTBE and the reaction mass was stirred for one minute at about 30oAnd then gave it to separate into a liquid phase. Then the lower aqueous layer was separated and the remaining organic layer was cooled to 17oC and washed with 50 ml of 10% aqueous Hydrosulphite solution of sodium, and then 50 ml of 20% aqueous sodium hydroxide solution and 50 ml portions

saturated aqueous solution of sodium sulfate to obtain a pH of 7-8. The product solution was dried over 5% by weight anhydrous MgS04and by filtering the spent desiccant received in the remainder of 14.7 g (88.6 per cent Teoreticheskaya at 1785 cm-1and the main carbonyl band carbonate or ether complex at about 1752 cm-1. The IR spectrum was only a trace of absorption bands HE. The product contained 4,48% active oxygen (theoretically 5,10%) according paroxetina method of determining the content of active oxygen, therefore the content of the product according to the results of the analysis accounted for 87.0%, and the adjusted output was 77,0%.

According to the production method, data output and data, IR spectrum, the product obtained by this reaction was specified in the header of the target product.

Example 14. Data exothermic effect at 280oF (138o(C) by the method of the SPI for polycaprolacton-Tris(mono-tert-butylperoxybenzoate), I-4

Unsaturated polyester resin in this example was a complex mixture of unsaturated polyester and styrene monomer. The unsaturated polyester was alkyd resin obtained by the esterification of the following components:

Component - Quantity (mol)

Maleic anhydride - 1,0

Phthalic anhydride - 1,0

Propylene glycol - 2,2

To the resulting resin was added 0,013% (by weight) hydroxynonenal inhibitor. Alkyd resin had an acid number of 45-50. Seven (7) parts of monomer. The obtained unsaturated polyester resin had the following properties:

Viscosity (Brookfield 2 at 20 rpm) is 13.0 P

Relative density - 1,14

Gelling and hardening properties of tert-butyl peroxybenzoate (a-2) (commercial peroxide product used for curing unsaturated polyester resins) and polycaprolacton-Tris(mono-tert-butylperoxybenzoate) 1-4 (new poly(nonoperational) of the present invention) was determined by the standard procedure of the Society of the plastics industry (SPI) to determine the exothermic effect of the proposed SPI methodology relating to the working of ectotherm for polyester resins, published in the signal instance of the materials of the 24th annual technical conference Reinforced Plastics/Composites Division, the Society of the Plastics Industry, Inc., 1969). According to this method at 280oF (138oC) was a comparative assessment a-2 and I-4. The number of used I-4 was equivalent in content of active oxygen of 1.0 g of pure A-2 to 100 g of unsaturated polyester resin.

The results of this study are given in the table for example 14 and show that the I-4 was ultinational and aterial resin faster than a-2, since the I-4 was more active in curing nanassy polymerization of styrene using the new poly(monoperoxyphthalate) as free-radical initiators

The polymerization of styrene was carried out using a monomer solution containing 95% styrene and 5% ethylbenzene (EB). As the initiators used 1,1-di(tert-BUTYLPEROXY)cyclohexane (a-3), i.e., Lupersol 331 (produced by Elf Atochem North America, Inc: commercial initiator, currently used to obtain high molecular weight polystyrene at elevated speeds of polymerization), 1,5-bis-(tert-butylperoxycyclohexyl)-5-oxapentane (a-4; known bis(monoperoxyphthalate); U.S. patent 3652631), polycaprolacton-bis(mono-tert-butyl-peroxocarbonate) (A-1) (known bis-(nonoperational); U.S. patent 5314970) and several poly(monoperoxyphthalate) of the present invention, namely, 1,1,1-Tris(tert - butylperoxycyclohexyl) ethane (I-1), 1,1,1-Tris (tert-butylperoxycyclohexyl)propane (I-2), polycaprolacton-Tris(mono-tert-butylperoxybenzoate) (I-3), polycaprolacton-Tris(menetret-butylperoxybenzoate) (I-4), 1,1,1-Tris[2-(tert-butylperoxycyclohexyl)ethoxy-methyl] propane (I-5) and polycaprolacton-tetrakis(mono-tert-butylperoxybenzoate) (I-6).

Preparation of solutions of styrene and initiator

To a solution of 95% styrene and 5% ethyl benzene at room temperature was added freely-radical,00252 mole of active oxygen per liter of styrene solution). The obtained styrene solutions were purged prior to sealing of glass ampoules (outer diameter 10 mm, inner diameter 8 mm) nitrogen.

Polymerization of styrene

Ampoules containing styrene solutions (several for each solution), was immersed in a circulating oil bath, the temperature of which was regulated with the help of the program temperature controller. The temperature of the samples was changed linearly from 100 to 151oWith the programmed speed 0,17oC/minute (5-hour program). Samples of each solution were removed from the bath with a 1-hour intervals during the 5-hour program and cooled by immersion in a water bath with ice. Then styrene solution was removed from the vials and analyzed to determine the mass-average molecular mass (Mw) polystyrene and residual styrene monomer.

Results

Characteristics of Tris(mono-tert-butylperoxybenzoate) I-1,I-2, I-3, I-4 and I-5 and tetrakis(mono-tert-butylperoxybenzoate) 1-6 were compared with the known compounds a-1, a-3 and a-4 in accordance with the above methodology. The results obtained are summarized in table for example 15.

Judging by the results concerning srednem the invention, i.e., I-1, I-2, I-3, I-4, I-5 and I-6 as initiators of the polymerization of styrene gave significantly higher values of Mw(330000-375000) after a 5-hour program of polymerization than those that were obtained with the known compounds a-1 (Mwapproximately 290000) And 3 (Mwequal to approximately 280,000) and a-4 (Mwapproximately 300000). Known bis(monoperoxyphthalate) A-1 was significantly less effective in increasing the molecular weight of polystyrene (the maximum value of Mwwas approximately 290000) than the Tris - and poly(monoperoxyphthalate) of the present invention (Mwapproximately 330000-375000). Thus, Tris - and poly(monoperoxyphthalate) of the present invention are a significant step forward in the field of polymerization ethylenedeamine monomers, such as styrene.

Example 16. Improved processes for the polymerization of styrene using poly (monoperoxyphthalate) as free-radical initiators

The polymerization of styrene was carried out according to the method described in example 15. Assessed as free-radical initiators in comparison with 1,1-di(tert-BUTYLPEROXY)cyclohexane (a-3) a few other poly(monoperoxyphthalate) Stronach) (I-9), polyester-Tris(mono-tert-butylperoxybenzoate) (I-10) of PLURACOL TP-740, polyester-Tris(mono-tert-butylperoxybenzoate) (I-11) of PLURACOL GP-730 and 1,5-bis(1,1,4-trimethyl-4-(tert-butyl-peroxy)antiperoxidase)-3-oxapentane (I-12). This example used the free-radical initiators in amounts equivalent 0,00277 mole of active oxygen per 1000 g of styrene solution (or 0,00252 mole of active oxygen per liter of styrene solution).

Polymerization of styrene

Ampoules containing styrene solutions (several for each solution), was immersed in a circulating oil bath, the temperature of which was regulated with the help of the program temperature controller. The temperature of the samples was changed linearly from 100 to 151oWith the programmed speed 0,17oC/minute (5-hour program). Samples of each solution were removed from the bath with a 1-hour intervals during the 5-hour program and cooled by immersion in a water bath with ice. Then styrene solution was removed from the vials and analyzed to determine the mass-average molecular mass (Mw) polystyrene and residual styrene monomer.

Results

Characteristics of poly (the methodology. The results obtained are summarized in table for example 16.

Judging by the results concerning the mass-average molecular mass (Mw) polystyrene, the use of poly(monoperoxyphthalate) of the present invention, i.e., I-7, I-9, I-10, I-11 and I-12, as initiators of the polymerization of styrene gave significantly higher values of Mw(300000-390000) after a 5-hour program of polymerization than those that were obtained with the known compound a-3 (Mwequal to approximately 280,000). In addition, at the end of the 5-hour period of residual styrene in the polystyrene obtained with the use of new poly(monoperoxyphthalate) of the present invention, were significantly lower than in polystyrene, obtained using a-3 (5-10% residual styrene vs. 17-18% residual styrene). Particularly attractive in this respect was the connection I-12. These results indicate that poly(monoperoxyphthalate) of the present invention are a significant step forward in the field of polymerization ethylenedeamine monomers, such as styrene.

Example 17. Improved processes for the polymerization of styrene using poly(monoperoxyphthalate) in combination with 1,1-di(tert-BUTYLPEROXY)the CEC is 95% styrene and 5% ethylbenzene (EB). This example used a modification of the method described in example 15. Were used a combination of two free-radical initiators, one of the initiators of the combination was new poly(nonoperational) of the present invention, namely, 1,1,1-Tris[2-(tert-butylperoxycyclohexyl)-ethoxymethyl]propane (I-5) or polyester-tetrakis (mono-tert-butylperoxybenzoate ) (I-7). The second initiator combinations was 1,1-di(tert-BUTYLPEROXY) cyclohexane (a-3), already known connection.

Preparation of solutions of styrene and initiator

Content combinations of free-radical initiators in this example were equivalent total 0,00230 mole of active oxygen per 1000 g of styrene solution (or 0,00209 mole of active oxygen per liter of styrene solution).

Polymerization of styrene

Ampoules containing styrene solutions (several for each solution), was immersed in a circulating oil bath, the temperature of which was regulated with the help of the program temperature controller. The temperature of the samples was changed linearly from 100 to 145,6oWith the programmed speed 0,19oC/minute (4-hour program). After a 4-hour period, the samples rest is Ali from vials and analyzed to determine the mass-average molecular mass (Mw) polystyrene.

Results

In the table, for example 17 shows the values of the mass-average molecular mass obtained by using a combination of A (1-5 and a-3) and In combination (I-7 and a-3) initiators as a free-radical initiator systems.

The results show that the mass-average molecular weight can be adjusted upward by replacing some part of the initiator And 3 initiator I-5 or I-7 or downward by replacing some part of the initiator I-5 or I-7 initiated a-3. Thus, polystyrene producers can use the new poly-(monoperoxyphthalate) of the present invention in combination with other free-radical initiators for regulating the molecular weight of the polystyrene and, therefore, control the physical properties of polystyrene.

Example 18. Improved processes for the polymerization of styrene using polyester-tetrakis(mono-tert-butylperoxybenzoate) (I-7) in combination with tert-butylperoxybenzoate (a-2).

The polymerization of styrene was carried out using a monomer solution containing 95% styrene and 5% ethylbenzene (EB). This example used a modification of the method, iniciatorov combination was a new poly(nonoperational) of the present invention, namely, the polyester-tetrakis(mono-tert-butylperoxybenzoate) (I-7), and the second initiator combinations was known nonoperated, namely tert-butyl peroxybenzoate (a-2).

Preparation of solutions of styrene and initiator

The total content of free-radical initiators used in this example were equivalent total 0,00277 mole of active oxygen per 1000 g of styrene solution (or 0,00230 mole of active oxygen per liter of styrene solution).

Polymerization of styrene

Ampoules containing styrene solutions (several for each solution), was immersed in a circulating oil bath, the temperature of which was regulated with the help of the program temperature controller. The temperature of the samples was changed linearly from 100 to 151oWith the programmed speed 0,17oC/minute (5-hour program). After a 5-hour period, the sample solution was removed from the bath and cooled by immersion in a water bath with ice. Then styrene solution was removed from the vials and analyzed to determine the mass-average molecular mass (Mw) polystyrene.

Results

In the table, for example 18 presents the values Srednerussky the individual initiating system.

The results show that the mass-average molecular weight can be adjusted upward by replacing some of the popular nonoperated a-2 initiator I-7 or downward by replacing some part of the initiator I-7 known nonoperation a-2. Thus, polystyrene producers can use the new poly (monoperoxyphthalate) of the present invention in combination with other sonoperoxone initiators for regulating the molecular weight of the polystyrene and, therefore, control the physical properties of polystyrene.

1. Poly(nonoperational) patterns AND

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where n is an integer from 2 to 8;

R1selected from tert-alkyl radical with 4 to 12 carbon atoms, 1,1,4-trimethyl-4(tert-BUTYLPEROXY)penciling radical, 1,1,4-trimethyl-4(tert-AMYLPEROXY)penciling radical, tert-cycloalkyl radical with 6-10 carbon atoms, tert-Uralkalij radicals from 9 to 13 carbon atoms and 3-methyl-1-butyl-3-yl and 3-methyl-1-pentyn-3-yl, with the proviso that when n= 2, R1selected from 1,1,4-trimethyl-4(tert-BUTYLPEROXY)penciling radical and 1,1,4-trimethyl-4-(tert-AMYLPEROXY)penciling radical;

i) when n= 2, R represents Brewster (n) and (o)

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< / BR>
where R9is alkilinity biradical with 2-8 carbon atoms;

ii) when n= 3, R represents triradical selected from 1,3,5-cyclohexatriene, R2C(CH2-)3, -CHR2CH(-)CH2and structures (a), (b), (C), (d) and (e),

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< / BR>
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< / BR>
where R2selected from hydrogen and alkyl radicals with 1-6 carbon atoms;

R3is triradical selected from R2C(CH2-)3, -CHR2CH(-)CH2and structures (a) and (b);

R4and R5are the same or different and selected from hydrogen and alkyl radicals with 1-4 carbon atoms;

x, y and z represent integers from 0 to 5, the sum of x, y and z is from 2 to 8;

r, s and t are integers from 0 to 6, the sum of r, s and t is from 3 to 18,

provided that when triradical R is an R2(CH2)3or the structure (b), R1is not tert-actiom;

iii) when n= 4 to 8, R represents polyradical selected from C(CH2-)4and structures (f), (g), (h), (i), (j), (k) and (1)

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< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
< / BR>
where R6is tetradecyl selected from C(CH2-)4and structures (f);

R7is biradical you the basis of sucrose, having the structure (m)

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p represents an integer from 1 to 3;

v represents an integer from 0 to 5; the sum of v, x, y, and z is from 3 to 10;

q represents an integer from 0 to 4; the sum of q, r, s and t is from 2 to 16,

and with the proviso that when R represents(CH2-)4, R1is not tert-actiom.

2. Poly(nonoperational) under item 1, in which n= 3 and R represents triradical selected from 1,3,5-cyclohexatriene, R2C(CH2-)3, -CHR2CH(-)CH2and the above structures (a), (b), (d) and (e).

3. Poly(nonoperational) under item 1, in which, when n= 4 to 8, R represents polyradical selected from C(CH2-)4and these structures (f), (g), (i), (j), (k) and (1).

4. Poly(nonoperational) under item 1, selected from 1,1,1-Tris(tert-butylperoxycyclohexyl)ethane, 1,1,1-Tris(tert-butylperoxycyclohexyl)propane, polycaprolactones(mono-tert-builderexception) with a molecular weight of from 600 to 1300, priepirtis(mono-tert-butylperoxybenzoate) and polyester-Tris(mono-tert-anilinoquinazolines) with a molecular weight of from 600 to 1200, polycaprolacton-tetrakis(mono-tert-butylperoxybenzoate) with molecular weight of about 1500, prefilters(mono-t0 to 1100 and 1,5-bis(1,1,4-trimethyl-4-(tert-BUTYLPEROXY)antiperoxidase)-3-oxapentane.

5. Poly(nonoperational) under item 1, in which n= 3 or 4.

6. Poly(nonoperational) under item 5, in which R is selected from the group consisting of R2C(CH2-)3and(CH2-)4and structures (a), (C), (d), (h) and (i).

7. Poly(nonoperational) p. 6, in which R' is selected from tert-butyl and tert-amyl.

8. Poly(nonoperational) under item 7, in which R represents the structure (s).

9. Poly(nonoperational) under item 7, in which R represents the structure (d).

10. Poly(nonoperational) under item 7, in which R represents the structure (h).

11. Poly(nonoperational) under item 7, in which R represents the structure (i).

12. The method of application of one or more poly(monoperoxyphthalate) according to any one of paragraphs. 1-11 as a free-radical initiator in initiating effective amount to initiate the free-radical reaction, selected from: A. polymerization ethylenedeamine monomer optionally in the presence of unsaturated elastomer; b. curing unsaturated polyesters; C. the crosslinking and curing of olefinic thermoplastic and elastomeric polymers; and E. modifying the molecular weight of polyolefins, Kotor/monoperoxyphthalate over time, sufficient for at least partial decomposition of the compounds for the implementation of free-radical reactions.

13. Method of application under item 12 for the polymerization of styrene monomer.

14. Method of application on p. 12 (hardening of unsaturated polyester resins, in which poly(nonoperational) selected from polycaprolactone-Tris(mono-tert-butylperoxybenzoate) with a molecular weight of from 600 to 1300.

15. The method according to p. 12 with stage a) or p. 13 using poly/monoperoxyphthalate in combination with at least one other peroxide or diperoxide selected from diarilpirimido, diphenoxyethane, complex peroxidation, monoisocyanates and dialkylamides in a period of time sufficient for at least partial decomposition of the specified combination peroxides.

16. The method according to p. 15, wherein the poly(nonoperational) selected from polyester-Tris(mono-tert-butylperoxybenzoate) with a molecular weight of from 600 to 1200 and polyester-tetrakis(mono-tert-butylperoxybenzoate) with a molecular weight of from 800 to 1100, and the initiator used in combination with poly(monoperoxyphthalate), choose from diphenoxyethane and slo is isproxy)cyclohexane.

18. The method according to p. 16, characterized in that the complex PROXIFIER is tert-butylperoxybenzoate.

Priority points and features:

23.08.1996 on PP. 1-18;

08.08.1997 on PP. 1-18 (clarification of signs).

 

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