Polyol-modified polymer, and method thereof

 

(57) Abstract:

The polyol used in the manufacture of polyurethane foams. Describes the polyol-modified aluminum a polymer obtained by polymerization of alumina with polyisocyanate with the isocyanate index in the range of 55 - 90 in the polyol, and the number of initial reagents provides a dry matter content of the stabilizer in the range of 1 to 15 wt.%, to use it as a stabilizer to obtain a polyol-modified polymer. Also described is a method of obtaining the polyol-modified polymer, the polymerization of alumina with polyisocyanate to polyol in the presence of added stabilizer, wherein the stabilizer is used as the polyol-modified aluminum a polymer obtained by polymerization of alumina with polyisocyanate with the isocyanate index in the range of 55 - 90 in the polyol when the number of source reagents, providing a dry matter content of the stabilizer in the range of 1 to 15 wt.%. The technical effect is to obtain a stable dispersion of grinding, allowing its use in obtaining polyurethane products, filling systems, coatings and adhesives. 3 S. and 8 C.p. f-crystals, 3 tables.

Polymer polyols are well known in science as a dispersion of solid polymer in the carrier-polyol, see, for example, J. of Cellular Plastics, March 1966, pages 84-96. They are particularly interesting from the point of view of their suitability inter alla (among other things) for special types of foams, such as elastomeric polyurethanes used as products such as interior trim of the vehicle and residential premises.

Used polymeric polyol is a dispersion of discrete polymer particles in the carrier-polyol, which is stable for a long time (preferably at least 6 months).

Used polymer polyol has a good processability and ideally gives a foam with a good degree of openness of the pores, i.e., not excessive degree of openness of the pores, which can cause the foam to destruction, and no small degree of openness of the pores, which can lead to shrinkage and to an unwanted quality of the finished foam.

Used polymer polyol is also able to be pumped by the pump in the traditional equipment for the production of foams. Although the experience of pumping technology means that potentially all poly is this dry matter content are some limits viscosity, to support the cost of pumping by the pump in a cost-effective limits.

So, for a typical dry matter content of 10 wt.% polymer polyol ideal viscous interval is from 600 to 2000 mPas (approximately 700-2100 CP) at 25oC. it was determined that direct production of 10 wt.% polymer polyol is not always gives the viscosity in the desired range and to seek ways of ensuring a higher dry matter content polymer polyols, which can be diluted with a compatible polyol carrier to 10 wt.% the dry matter content of the polymer polyol having a viscosity in ideal viscosity range.

Description British patent N A is polyol-modified polymer obtained by polymerization of alumina, especially alkanolamine, with an organic polyisocyanate in the presence of a polyol. The dry matter content of the dispersions obtained in this way is provided in the document in the range of about 1-35% by weight.

These dispersions are supplied as a so-called "PIPA (PIPA)-" polyol dispersion polymer polyols, and usually get a polymeric polyol using in the quality of the m dry matter, with further dilution with a polyol to obtain a lower desired dry matter content.

It was found that whereas in accordance with GB-A-2072204 you could get up to 20 wt.% polymer polyol when using the preferred catalyst, dibutyltindilaurate, it was impossible to obtain a 30 wt.% polymer polyol. Moreover, when using octoate tin (II) as catalyst, alternative catalyst tin, mentioned in GB-A-2072204, it was impossible to get even 20 wt.% polymer polyol.

Description of the European patent N 79 115B offers highly concentrated polyol-modified polymer, the reaction of MDI with tert-N-polyamines in the presence of a polyol and then adding an excess of MDI to achieve the specified ratio of isocyanate groups to hydroxyl groups with obtaining the specified high solids content of the dispersion polymer polyol.

The dry matter content of such polymer polyols is in the range from 40 to 80 wt.%, especially preferred is 50% dry matter. If necessary, the polymer polyols with lower dry matter content, Takenaka ways, however, can result in excessive crosslinking, and requires great care to avoid too high viscosity or gelation of the product.

Patent EP-B-79115 shows the various precautions that are necessary in order to avoid gelation, and indeed the necessity of separately controlled add a part of the isocyanate in order to avoid gelation in a large scale.

Another type of polyol-modified polymer, it is proposed in the Description of the International patent WO 92/02567, according to which, despite alamin used in solid phase, althofen, with the increase of fire proofing characteristics derived from them foams.

A method of obtaining a polymer polyol is a direct reaction Atofina and isocyanate in the presence of polyol, and in the examples are obtained dispersion with a dry matter content ranging from 7 to 16 wt.% and with the variation of the viscosity, which is usually at a high level. The main polyol may be a polyol, polymer-modified; in the example below we are using a polyol modified styrolacrylonitrile polymer, and is 0 JV.

It was established the possibility of obtaining a stable dispersion polyol modified aluminum polymer having about 30 wt.% the dry matter content, a simple method that uses forprimary stabilizer.

Under the "prepolymer" refers to a molecule, which can be combined with other traditional methods of connection polymers.

In accordance with the present invention provides a method of obtaining a polyol-modified polymer, which (way) contains a polymerization alumina with polyisocyanate in the presence of a polyol and a stabiliser, which itself is a polyol modified aluminum polymer.

Adding stabilizer provides a level of introduction of the primary polyol, which is sufficient to obtain a stable dispersion. It is assumed that the stabilizer comprises a reactive products, which participate in reactions in the method of the invention.

The stabilizer thus chemically involved in the method of obtaining and does not remain inert as stabilizers offered for other polyol as one of the systems, modified polymer, such as those isochrony polymer" is used, vzaimootmenyaemye alternative name "polymer polyol".

You can use any polyol, polyisocyanate or alamin, suitable for use in the manufacture of polyurethanes. Such polyols and polyisocyanates are well known to experts in the field of technology of polyurethanes and widely described in the literature.

Thus, the polyol used in the method of the invention or the stabilizer may be a polymeric polyol such as a simple polyester, simple polythioether, complex polyester, complex polyetherimide, Polyacetal or polycarbonate or a mixture thereof, having a molecular weight in the range from 200 to 16000.

Of particular interest, however, are polyester polyols having a molecular weight of from 200 to 10,000, especially from 1000 to 10000, such as described in British patent N 1482213. Accordingly, they are polyoxyalkylene polyols obtained by the interaction of accelerated or mixture of alkalisation with an initiator containing active hydrogen.

Polyethers polyoxypropyleneglycol with ethylenoxide terminal groups are especially used for the manufacture of elastomeric penopoliuretana or block copolymers.

Organic polyisocyanates (i.e. organic isocyanate having two or more isocyanate groups), which can be used in the invention include aliphatic, cycloaliphatic, analiticheskie, aromatic and heterocyclic polyisocyanates.

Of particular interest are the aromatic polyisocyanates, for example, colorvision (TDI = TDI) and diphenylmethanediisocyanate (MDI = MDI), which are mass-produced in a fairly clean and untreated. More precisely, they include 2,4 - and 2,6-colordistance and mixtures thereof; difenilmetana-2,4'-diisocyanate and their mixtures (usually referred to as pure MDI), for example, a mixture containing from 70 to 100%, especially 80%, by weight, of 4,4'-isomer and from 0 to 30%, especially 20%, by weight, of 2,4'- isomer; mixtures of MDI with polyvinylpolypyrrolidone received by postironium mixture of polyamines obtained by or aniline with formaldehyde (usually referred to as crude or polymeric MDI); and mixtures of TDI and MDI, clean or dirty, for example, a mixture containing 60% by weight of TDI and 40% by weight of MDI.

Can also be used diisocyanates modified in a known manner by the introduction of significant caliceti used, include prepolymers with isocyanate end, for example the reaction products of a diisocyanate with a lack of one or more low molecular weight polyols, such as trimethylolpropane, dipropyleneglycol or tripropyleneglycol; and polyisocyanate, polyisocyanurate and mixtures thereof.

In order to make sure to avoid excessive crosslinking preferably, in the method of the invention or to obtain stabilizer was used, the polyisocyanate with the isocyanate index in the range from 55 to 90, preferably 67-80.

Alumina are defined as organic compounds having one or more hydroxyl groups and one or more amine group can be any of those specified or described in GB-A-2072204.

Relevant examples of Alaminos are monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-acylethanolamine, N-butylethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisophthalic, N-ethylisopropylamine, N-propylnorapomorphine.

Can also be used substituted alkanolamine. The preferred alkanolamine is t is retene can be catalyzed by use of any conventional catalyst for polyurethane chemistry. Such catalysts include tertiary amines, such as, for example, triethylenediamine, N-methylmorpholin, diethylethanolamine and dimethylbenzylamine; tertiary phosphines, such as trialkylphosphine and dialkylanilines; strong bases, such as hydroxides of alkali and alkaline earth metal alcoholate and reaction; salts or organic acids such as sodium acetate, octoate tin, tin oleate and octoate lead; and ORGANOMETALLIC derivative, such as described U.S. patent N 2846408.

In the modified polymer polyol obtained in accordance with the invention may be introduced for other traditional ingredients used for the manufacture of polyurethane foams, such as surfactants, cross-linking or lengthening the chain of agents, additives regulating the pore size and structure, for example, silicone oil or polysiloxane copolymers with polyalkyleneglycol, foaming agents, fillers, pigments, plasticizers and flame retardants, for example halogenated aminophosphate and melamine.

Regarding flame retardants, it is possible that alvastin can be used instead of or in combination with aluminum to obtain a stabilizer and/or foliolosa detail in WO 92/02567.

It should be noted that the polyol, the polyisocyanate and alamin used to obtain stabilizer and subsequently to obtain a polyol-modified polymer may be the same or different.

Preferably, as raminosoa component for receiving the stabilizer, and to obtain a polyol-modified polymer is used triethanolamine. The preferred polyisocyanate in both cases is isocyanate-based TDI either in pure form or in the form of 80/20% by weight mixture of 2,4 - and 2,6-isomers colordistance.

It is preferable to obtain two products use different types of polyol and catalyst.

Especially good results are achieved when using a polyol with high reactivity for receiving the stabilizer. This high reactivity allows more polyol to enter into a stable polymer dispersion.

Relevant examples of polyols with high reactivity are polyethers of polyoxypropyleneglycol with integral ethyleneoxide groups, having a content of ethylene oxide, preferably from 10 to 20 wt. %. Shiro was designated as CARADOL MD 1078) firm shell.

Polyethers of polyoxypropyleneglycol with integral ethyleneoxide groups are also suitable for use to obtain a polyol-modified polymer, preferably having a content of ethylene oxide is from 10 to 20 wt.%, especially less than 15 wt.%. Such polyol sold under the trademark KARAGOL (CARADOL) MS 36 - 3 (originally as CARADOL 36-3) firm SHELL.

Although any catalyst is suitable for use in the present invention is very suitable results provide catalysts based on tin. As examples of suitable catalysts based on tin can be specified octoate tin, tin oleate, tin stearate, dibutyltindilaurate, dibutylamino-2-ethylhexanoate.

It is preferable to use dibutyltindilaurate to obtain stabilizer. Octoate tin is preferred as the catalyst to obtain a stable with a high dry matter content of the modified polymer polyol method of the invention, and unexpectedly it was found that with octoate tin even with 20 wt.% dry matter content of the polymer polyol can be obtained non-stabilized direct by patent GB-A-am way described in GB-A-2072204, and amount of starting materials are selected so that the stabilizer, respectively, has a dry matter content ranging from 1 to 15 wt.%.

Preferably, the dry matter content of the stabilizer is in the range from 6 to 8 wt.%. The amount of stabilizer used in the method of the invention preferably is in the range from 1 to 15 mass parts, especially 4-10, relative to the total mass of the reaction components.

The number and ratio of components to obtain a polyol-modified polymer by the method of the invention are selected depending on the desired final dry matter content and viscosity of the product (viscosity level depends on the content of dry matter). The method of the invention is particularly suitable for the production of polymeric polyols having a dry matter content up to 50 wt.%, especially preferred is a content of dry substance equal to 30 wt.%.

Polymer polyol with 30 wt. % dry matter content can be used directly with the appropriate processing equipment to produce polyurethane foam. However, for most applications it is preferable Razboinik from polyol, already used in the polyol, a modified polymer, with a more traditional dry matter content of from 10 to 15 wt.%.

PIPA polyol, commercially available under the trademark KARAGOL (CARADOL) SP 50-01, represents a received direct way of polymeric polyol with 10 wt.% the dry matter content having a viscosity of 2300 CPS (at 25oC.

When diluted to 10 wt.% dry solids polymer polyol obtained by the present invention may be a polymer polyol having a viscosity up to 1000 CP. This is an advantage and provides more efficient processing for mass production of polyurethane.

The reaction for obtaining modified polymer polyol, and indeed, the reaction of obtaining alamin-modified polymer polyol as one stabilizer may be carried out by mixing the reactants with stirring at a temperature in the range from 0 to 100oC, but usually at room temperature. The reaction is exothermic. Can be used a simple periodic process or can be used for continuous in-line mixing of the components.

Naturally, the stabilizer may be fresh and used directly in the joint venture is ECC. As the stabilizer, however, is itself a stable dispersion of a polymeric polyol, it can be obtained at different time or in a different location and stored until needed.

Modified polymer polyols obtained in accordance with the invention, are used to obtain a variety of polyurethane products, in particular, foams and especially highly elastic foam or elastomeric foams with a modified Flammability; injection systems; systems coatings and adhesive systems.

The invention will now be illustrated by examples, in which examples 1 and 2 show the receipt thermopolymeric stabilizer. Examples 3 through 5 show the preparation of stabilized polymer polyols of the present invention, and examples 6 and 7 are comparative examples.

In the examples, the symbol "PM" indicates "Mass parts (parts by weight), and commercially available polyols and diisocyanate used have the following characteristics:

KARAGOL (CARADOL) SA 36-01 - polyetherpolyols based on activated propylene oxide/ethylene oxide supplied by the company SHELL, which is a triol based on glycerol containing 17 wt.% of ethylene oxide; the middle is virovanny glycerine triol, supplied by the company SHELL, containing 13 wt.% of ethylene oxide; mass-average molecular weight of 4500 and a hydroxyl number of 36 mg KOH/g polyol.

KARAGAT (CATADATE)80 - 80/20 wt.% a mixture of 2,4-2,6-colordistance.

CARADOL and KARAGAT - brand.

In the examples used for the diisocyanate is given isocyanate index. Index 100omeans that the number of available isocyanate groups is sufficient to react with all the hydroxyl groups. As for the stabilizer and the polymer polyol of the present invention the isocyanate index, expressed in the examples are given in relation only to triethanolamine, i.e., the primary hydroxyl group of polyol are not included.

Viscosity (CP: centipoise) given in the examples are determined by standard methods using a viscometer Ferranti-Shirley Cone and Plate.

Example 1

Under continuous stirring, mix the following ingredients, PM:

CARADOL SA 36-01 - 92,28

Triethanolamine - 3,33

KARAGAT -80 - OF 4.38

Dibutyltindilaurate - 0,01

Used triethanolamine 98% purity; dibutyltindilaurate DABCO T-12 company Air Products is used in the form of a 5% solution in the polyol; an isocyanate index of the first substance 7,72 wt.%.

Example 2

This example is similar to example 1, but with the following proportions of the reagents PM:

CARADOL SA 36-01 - REPOSSESSED A 93.44

Triethanolamine - 2,73

KARAGAT -80 - 3,82

Dibutyltindilaurate - 0,01

Isocyanate index CAREDATA-equals 80 80o.

The product is obtained with a viscosity 2950 CPS (at 25oC and dry matter content 6,56 wt.%.

Example 3

Performed a series of experiments in which continuous stirring mix together different amounts Caradol MS 36-03, triethanolamine, Caredata-80, octoate tin (used in the form of a product supplied by the company Air Products under the trademark DABCO T-9) and stabilizer, obtained as in example 1 to obtain a polymer polyol with a dry matter content of 30 wt.%, which in each case is stable over a long period of time, without vicadine solid.

Each polymer polyol is used to obtain the elastic tiled foams according to the traditional technology with diisocyanate KARAGAT-80. Characteristics of processing AIDS (processability) of the obtained foams are monitored and evaluated visually. The principal in the evaluation of recyclable who ytou are provided below in table 1.

Example 4

Using the methodology of example 3 is the number of polymeric polyols with a dry matter content of 30 wt. % when using the stabilizer of example 2 together with CARDOMOM MS 36-03, triethanolamine, CARDAMOM-80 and actuator tin (DABCO N-9). Each polymer polyol is stable over a long period of time without precipitation of solids.

Again from each sample polymer polyol obtained tiled foam as in example 3 and evaluated processability foam.

The 23 results of the experiments are given in table 2.

Commercially available styrene/Acrylonitrile polymer polyol (supplied under the trademark VARALUX HN 202 by the company Dow) gives a rating of processing AIDS foam "good" for the same estimation technique.

The results of examples 3 and 4 show that all of the polymer polyols of the present invention provide acceptable processability foam; there is no or only a small degree of shrinkage of the foam.

Example 5

Repeated receipt of polymer polyol sample XXXI of example 4 on a larger scale (4 kg). Then, portions of the polymer polyol content of dry substances the substances. Is determined by the viscosity of the undiluted and the diluted polymer polyols; the results are given in table 3.

Example 6

In this example, polymeric polyols with a high dry matter content obtained by the method presented in the description of the British patent N 2072204A, using dibutyltindilaurate as a catalyst.

Amounts of reactants and viscous properties are given in table 4.

Example 7

Here we describe an attempt to obtain a polymer polyol with 20 wt.% the dry matter content in accordance with the method of the patent GB-A-2072204, but using octoate tin as a catalyst.

CARADOL SA 36-01 - 79,79 PM

Triethanolamine - 9,38 PM

KARAGAT-80 (index 66o) - 10,78 PM

Octoate tin - 0,05 PM

The dry matter content of 20 wt.%

The viscosity at 25oC - Indeterminate

Observed sedimentation of solid particles in the form of large agglomerates, which were separated from the polyol when standing.

Example 6 is obtained polymer polyol with 20 wt.% the content of dry substances in a known manner using the preferred catalyst of the patent GB-A-2072204, but not obtained polymer polyol F (II) 't even suitable polymeric polyol with 20 wt.% the dry matter content when using the method of the patent GB-A-2072204, as shown in example 7.

1. A method of obtaining a polyol-modified polymer, the polymerization of alumina with polyisocyanate to polyol in the presence of added stabilizer, wherein the stabilizer is used as the polyol-modified aluminum a polymer obtained by polymerization of alumina with polyisocyanate with the isocyanate index in the range of 55 - 90 in the polyol when the number of source reagents, providing a dry matter content of the stabilizer in the range of 1 to 15 wt.%.

2. The method according to p. 1, characterized in that aluminum is triethanolamine.

3. The method according to p. 1 or 2, characterized in that the stabilizer is obtained using a simple polyester polyoxypropyleneglycol with integral ethyleneoxide groups, having a content of ethylene oxide in the range of 10 to 20 wt.%.

4. The method according to PP.1 to 3, characterized in that the polyol is a simple polyester polyoxypropyleneglycol with integral ethyleneoxide groups, having a content of ethylene oxide in the range of 10 to 20 wt.%.

4. The method according to p. 4, characterized in that the polyol is a simple polyester polyoxypropyleneglycol with integral ethyleneoxide groups having from the RA to obtain stabilizer used dilaurate dibutylamine.

7. The method according to PP.1 - 6, characterized in that as a catalyst to obtain a polyol-modified polymer, use octoate tin (II).

8. The method according to PP.1 to 7, characterized in that use 4 - 10 wt.h. stabilizer calculated on the total weight of the reaction components.

9. The method according to PP.1 to 8, characterized in that the polyol, polymer-modified, diluted with additional polyol after receipt.

10. Polyol-modified polymer obtained by the method according to PP.1 to 9, used to obtain polyurethane products, filling systems, coatings and adhesives.

11. Polyol-modified aluminum a polymer obtained by polymerization of alumina with polyisocyanate with the isocyanate index in the range of 55 - 90 in the polyol, and the number of reaction components ensures that the dry matter content of the stabilizer in the range of 1 to 15 wt.%, to use it as a stabilizer to obtain a polyol-modified polymer.

 

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