GB2107330A - Process for obtaining polymer/polyol products - Google Patents

Abstract

Vinyl copolymers in a polyhydroxyl solvent for use in the production of polyurethanes are produced by polymerising a mixture of monomers containing 70-90% acrylonitrile, 9-12% styrene and 1-9% of another vinyl monomer, preferably methylmethacrylate, in the presence of a free-radical catalyst and in a polyhydroxy compound, e.g. ethylene glycol, ethylene oxide/propylene oxide copolymer initiated by poly (active hydrogen) compound. The polymerisation is characterized by being effected at first under vacuum, with the pressure being allowed to increase slowly as the reaction proceeds. Monomers may be introduced continuously, with finally a heating stage to complete polymerization.

Description

SPECIFICATION Process for obtaining vinyl co-polymers A polymer is a large molecule made up by the repetition of other smaller and simpler ones, known as monomers. The polymers are formed by means of two types of reaction, poly-addition and polycondensation.

The poly-addition reaction is that involving chain reactions in which the chain in course of formation is produced through an ion or a substance with an unmatched electron known as a free radical. Generally, the free radical is formed by decomposition in relatively unstable material known as the initiator. The free radical is able to react to open the double bond of a vinyl monomer and add itself thereto, with a residual unmatched electron. In a very short period (generally seconds or less), many monomers are successively added to the growing chain. Finally two free radicals react, cancelling their reactivity and forming one or more polymer molecules. Polyvinyl polymers are subject to this type of reaction. They are subdivided under the headings of homopolymers and copolymers.The first are formed from a single monomer and representative examples are: polyacrylonitrile, polystyrene, methyl polymethacrylate, etc.. The second are formed from two or more monomers such as: polyacrylonitrilestyrene, polyethylene-vinyl acetate, polyacrylonitrile-styrene-methylmethacrylate, etc..

The polycondensation reaction occurs with two poly-functional molecules giving rise to a polyfunctional molecule, with the possible elimination of small molecules such as water. The reaction continues until at least one of the reagents used is exhausted; a balance is usually established, which can be displaced by raising the temperature or controlling the quantity of reagents used. This type of reaction comprises polymers such as ethylene glycol, polyether phthalate, polyamides, polyurethanes, etc..

There are other compounds which are difficult to classify such as polyethoxylates and polyol ethers of alkylene oxides; as they can be considered as obtained by poly-addition reaction, since they do not start from a monomer, and require at least one compound with active hydrogen molecules, as well as the reaction not being very fast as otherwise normally encountered in this type of reaction. They can also be considered as formed by poly-condensation reaction, since they do not form residual compounds and the reaction occurs as an addition of more monomers, alkylene oxide.

This document deals with the synthesis and application of a type of polymer obtained by polyaddition through a system of free radicals.

The polyaddition reactions are subdivided into homogeneous and heterogeneous polymerisations.

The first are those in which the initial reaction mixture is homogeneous and in the second they are not.

Some homogeneous systems can become heterogeneous as the polymerisation proceeds, owing to the insolubility of the polymer within the reaction medium. Homogeneous polymerisations can occur in the solid or in the solution form, and heterogeneous polymerisations occur in suspensions and emulsions.

This description deals with homogeneous polymerisations in solution.

Vinyl polymerisation is an exothermic process since it involves the transformation of the 7r and T bonds; the polymerisation energy depends upon the nature of the groups adjacent to the carbons which carry the double bond, which may assist in breaking the said double bond by inductive or conjugated effects (Table 1).

Table 1 - heat of polymerisation Monomer Structural unit AHp, Kcal/mol 1. Ethylene -CH2-CH2 22.7 2. Propylene -CH2-CH(CH3)- 20.5 3. Isobutylene -CH2-C(CH3)2- 12.3 4. Butene-1 -CH2-CH(C2H5)- 20.0 5. Isoprene -CH2-C(CH3)=CH-CH2- 17.4 6. Styrene -CH2-CH(C6H5)- 16.7 7. a -methyl styrene -CH2-C(CH3)(C6H5)- 8.4 8. Vinyl chloride -CH2-CHCl- 22.9 9. Vinyl acetate -CH2-CH(C2H3O)- 21.0 10. Acrylonitrile -CH2-CH(CN)- 18.4 11. Methyl methacrylate -CH2-C(CH3)(C2H302)- 13.5 12. Ethyl acrylate -CH2-CH(C3H5O2)- 18.8 13. Methyl acrylate -CH2-CH(C2H302)- 1 8.8 14.Acrylamide -CH2-CH(CONH2)- 19.8 Polymerisation in solution avoids many of the block polymerisation disadvantages. The solvent serves as a diluent and assists the polymerisation heat dissipation, and furthermore its presence allows easier stirring by reducing the viscosity of the medium. Thermal control is much easier in polymerisation in solution, than block polymerisation for instance.

The kinetic diagram of free radical polymerisation is shown in the following manner: Initiation I - 2 R R + M - P Ri Propagation Pn. + M-Pm + I. KpPm. M Transfer Pm. + M-M' + Polymer kfm P. M Re-initiation M. + M-Pi KpmMM Termination P. + P.-Polymer Ktp. Where I, M and P are the concentrations of initiator, monomer and polymer, R', M and P. are the concentrations of radicals derived therefrom, and Kp, Kfm and Kt are the coefficients of velocity.

The versatility of polymers obtained by polymerisation in solution is widely varied. For that reason, it was considered that a type of such compound could be obtained which would be applicable to our required field of activities and polyurethane polymers were used. These polymers are obtained by reaction of a compound with polyhydroxyl groups and another with polyisocyanate groups. There is a correlation between the chemical structure of initial compounds and the physical properties of the final compound. An analysis of the following factors will be undertaken: a) Intermolecular forces, also known as secondary chemical bonds' are the result of the formation of hydrogen bridges, bipole moments, polarisability and Van der Waals forces.These intermolecular forces tend to link chains similarly with primary chemical bonds, thereby increasing tensile strength, tearing strength, hardness and vitreous transition temperature, for example in polyacrylonitrile and poiymethyl methacrylate b) The rigidity of the chains originates mainly from rigid structures such as aromatic rings, for instance styrene. Logicaily, rigidity favours hardness and tensile strength but reduces elasticity. c) The greater the crosslinking, the greater will be the hardness and the lower will be the flexibility.

Bearing these premises in mind, it is possible to design one of the two compounds, isocyanate or polyhydroxyl, which allows polyurethanes suited to our needs to be created.

Since isocyanate is a highly reactive compound to very many compounds, such as ambient humidity, it is preferable to use the polyhydroxyl compound.

The idea outline in this document is to obtain vinyl polymers by way of polymerisation in solution, dissolved in a polyhydroxyl compound in such a manner as to obtain a final reactive composition through hydroxyl groups in the presence of isocyanate and with a series of physical properties conferred by the vinyl polymer.

Certain compositions of this type have already been developed and have been encountered in previously published literature and patents.

In principle, polyacrylonitrile polymers have been used in various types of polyhydroxylate compounds. The following patents can be quoted for instance: U.S. patent 3 304273 (14th Feb. 1966) British patent 1 040 452 (24th Aug. 1966) Belgian patent 643340 (1st June 1964) At a later date, polyacrylonitrile-styrene copolymers have been synthetically produced in polyhydroxylate compounds, as described in the following patents:: Canadian patent 785 835 Belgian patent 788 11 5 German patent 1152 536 and 1152 537 In our case, three acrylonitrile styrene and methyl methacrylate monomers were used, selected according to their chemical structure and influence upon physical properties as quoted in previous paragraphs.

Polyacrylonitrile combines strong polarity and the small volume of the -C-N group, which is translated into a high intermolecular strength. At the same time there is a high solubility parameter, producing a high resistance to organic solvents.

Polystyrene has aromatic rings, and consequently a high rigidity as well as intense intermolecular strength. Its thermal conductivity is very low. It is inert to many inorganic reagents.

Methyl polymethacrylate combines high rigidity and hardness properties together with strong aging resistance. At the same time it will withstand inorganic reagents, with the exception of inorganic acids.

In view of the facts outlined in the above three paragraphs, the synthesizing of a copolymer was considered, comprising the three monomers in suitable proportion to give optimum balance between the various properties. The said copolymer was synthesized in solution using, as a solvent, a polyhydroxyl compound with a view to providing the hydroxyl groups intended to react at a later stage with the polyfunctional isocyanates.

The present invention describes the polymerisation in solution of a vinyl copolymer consisting of 248% of acrylonitrile, 1.5-4.5% of styrene and 0.51.5% of methyl methacrylate, using as a solvent a polyhydroxyl compound with a molecular weight of 2,000 to 8,500 and a catalyst generating free radicals.

The novelty in this invention is to achieve the reaction in the absence of a nitrogen flow, ensuring a prior vacuum and allowing the pressure to increase slowly as a further quantity of monomers is added.

In this way, the pressure generated within the reaction vessel favours the conversion of the fraction of monomers in the gaseous state into polymers.

The polyhydroxyl compounds used as solvents are products obtained following reaction by basic or acid catalysis, polyfunctional initiators with active hydrogen molecules such as monoethylene glycol, monopropylene glycol, diethylene glycol, 1 ,3-dihydroxypropane, 1 ,3-dihydroxybutane, 1.4 dihydroxibutane, 1 ,2,6-hexanetriol, glycerine, trimethylolpropane, pentaerythritol, sorbitol, sucrose, neopentyl glycol, monoethanolamine and diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethylene diamine, tolylenediamine, 1,1 O-dihydroxydecane and 1,2,4trihydroxybutane.

The most used alkylene oxides are of the ethylene, propylene, styrene and butylene type, in homopolymer or copolymer form, the latter in block, random or alternating.

The basic catalysts used are: sodium hydroxyde, potassium hydroxide, sodium methoxide, calcium oxide, alkaline carbonates, alkaline salts of fatty acids, dimethylamine, triethylamine, certain organo metallic compounds, etc...

The acid catalysts used are boron trifluoride, tin chloride, titanium chloride, aluminium sulphate, benzoyl chloride, acetic anhydride, boric acid, sodium bisulphate, boron tribromide, etc...

It is considered in this case that the most suitable polyhydroxyl compounds are those having a molecular weight averaged by the determination of functional groups, between 2x 103 and 8.5x 103 and mainly those between 3x103 and 6.5x103.

The compounds described in this patent are used to obtain polyurethane cellular compounds, requiring reaction with polyisocyanates in the presence of specific catalysts.

In preparing cellular polyurethane compounds, whether flexible or with a high resilience, it is essential to ensure strict stoichiometric ratios, i.e. using a slight excess only as a maximum, in relation to the stoichiometric needs of organic polyisocyanate. In other words, the reagents, polyisocyanate and polyhydroxyl compound, are used in relative amounts which are such that the proportion between -NCO total equivalents and total active H equivalents is approximately 0.8 to 1.5, preferably 0.9 to 1.2. This proportion is known as the isocyanate index and is expressed as a percentage of the polyisocyanate stoichiometric amount required to react with the total active H molecules.

The organic polyisocyanates used to produce polyurethanes are organic compounds containing at least two isocyanate groups. These compounds are well known and the most suitable types include hydrocarbon diisocyanates (for instance alkylene diisocyanates and arylene diisocyanates) such as: ethane 1 ,2-diisocyanate, butane-1 ,4-diisocyanate tolylene-2,4-diisocyanate; tolylene-2,6, diisocyanate;o-xylene- 1 ,3-diisocyanate, 1 -chlorobenzene-2,4-diisocyanate; 1 -nitrobenzene-2,5- diisocyanate; 4,4'-diphenyl methylene di-isocyanate; 3,3'-diphenyl methylene -- di-isocyanate and polymethylene -- poly (phenylene di-isocyanates).

The catalysts suitable for the production of polyurethane according to this invention include: ternary amines such as trimethylamine; triethylamine; tributylamine; N-methyl morpholine; N-ethyl morpholine: N-comorpholine; N,N,N',N'-tetramethyl-1 ,3-butane diamine; 1 ,4-diazobicyclo-(2,2,2)- octane; pyridine oxide; N,N,N',N'-tetramethyl ethylenediamine, N-methyl-N'-dimethylamino ethyl piperazine; N,N-dimethylbenzylamine, bis-(N,N-diethylamino ethyl) adipate, N,N diethylbenzylamine; pentamethyl diethylene tetramine; N,N dimethylcyclohexylamine; N,N-dimethylphenyl ethylamine, 1,2- dimethylimidazole, 2-methylimidazole.

Ternary amines carrying atoms of hydrogen active with respect to isocyanate groups, such as triethanolamine, triisopropanolamine, N-methyl diethanolamine, N-ethyl diethanolamine, N,N-dimethyl' ethanolamine as well as its reaction products with alkylene oxides. Nitrogenous bases are also taken into consideration, such as tetra alkylammonium hydroxides; alkaline hydroxides such as sodium hydroxide, alkyl phenates such as sodium phenate or alkaline alcoholates, such as sodium methylate.

The catalyst for this amine is present in the reaction mixture of final urethane production in quantities of 0.05 to 3 parts by weight of active catalyst, for each 100 parts by weight of the polyhydroxyl reagent. Normal procedure is to include a small amount of certain metallic catalysts as an additional component to the reaction mixture, to favour the gelling of the foam-forming mixture.

Catalysts of this type most commonly used are organo-metallic compounds, specially tin organic compounds. Preferably carboxylic acids tin (II) saits, such as tin (II) acetate, tin (il) octoate, tin (II) ethylhexoate and tin (II) iaurate and tin (IV) compounds, for instance dibutyl stannic oxide, and dichlorodibutyl tin (IV), dibutyl stannic diacetate, dibutyl stannic dilaurate. They may be used in the pure form or as mixtures, the amount of such metallic co-catalysts being such that the reactive mixture contains between 0.05 to 2 parts approximately by weight per 100 parts by weight of polyhydroxyl reagent.

Formation of the cellular compound is achieved by the presence in the reaction mixture of variable amounts of blowing agent or propellant. The basic medium is water which, as a result of reaction with isocyanate, generates carbon dioxide 'in situ'. Organic propellants are also used, such as acetone, ethyl acetate, alcano halogens -- substitutes such as methylene chloride, chloroform, vinyledene chloride, monofluorotrichloromethane, dichlorofluoro methane as well as butane, hexene, heptane or di-ethyl ether.

These reagents vapourise as a result of the heat generated during the reaction. The generally preferred method is to use water alone, or a combination of water and a fluorohydrocarbon propellant.

The amount of propellant used varies in accordance with the required density and hardness.

Stabilisers are also used in the production of cellular polyurethane, and these are selected with reference to a particular type of foam. The surface-active reagent maintains the original foam level once it is formed. Foams produced with suitable surface-active reagents are subject to a minimal humidification or relaxation in the upper part. According to this invention, stabilisers for the purposes outlined here comprise hydrosoluble polyol ether siloxanes formed as an example, by combining an ethylene oxide and propylene oxide co-polymer with a polydimethyl siloxane residue or generally by 'hydrolysable' polysiloxene-polyoxyalkylene block co-polymers as described in U.S. patents 2 834 748 and 2 917 480, as well as block non hydrolysableX polysiloxane-polyoxyalkylene co-polymers as described in U.S. patent 3 505 377.

Other examples of surface-active additives and stabilisers, as well as cell controllers, reaction retardants ignition inhibiting substances, plasticisers, colorants and fillers, conditioners, fungicides, and bactericide materials, together with numerous details concerning the use and operation of such additives, are outlined in the Plastics Yearbook Kunststoff-Handbook Vol. VII, edited by Vieweg and Hijchtlen, Carl Hanser Verlag, Munich (1965).

The vinyl monomers used in the production of compounds described in the invention are utilised in amounts of 5 to 30% by weight related to the final product. The most suitable are those with 1 5 to 25% of vinyl monomer mixture as related to the total. The most apt monomer mixtures in relation to the balance of properties are those containing 70 to 90% of acrylonitrile, 21 to 9% of styrene and 9 to 1% of methyl metacrylate.

The most used free radical-forming catalysts are compounds such as azobisisobutyronitrile; di(ethyl hexyl) peroxydicarbonate; di-isopropyl peroxydicarbonate; di-isopropyl peroxydicarbonate; terciobutyl perox pivalate, pelargonyl peroxide, acetyl peroxide, benzoyl peroxide, tert-butyl peroxyacetate; tert-butyl hydroperoxide, etc. The amounts used vary between 0.05 and 2.0% by weight related to the product obtained.

The catalyst selection is a function of the conversion required in relation to the solvent, polyhydroxyl compound, as an example, whereas there is practically no chain conversion with azobisisobutyronitrile it is very considerable with benzoyl peroxide. The chain conversion results in a branch grafted onto the tertiary carbon atoms of the oxypropylene treated chain of the polyhydroxylic compound.

The reaction temperature is a function of the molecular weight of the vinyl polymer required, so that when the temperature is low, the polymer has a high molecular weight, with a high viscosity in consequence; as the temperature is raised the polymer grows slightly and the viscosity is reduced. Tests show that the optimum temperature range is between 1 10" and 1 2O0C.

A number of examples relating to the synthesis of compounds is quoted below: EXAMPLE 1 This features 6,500 g of polyhydroxyl compound consisting of an initiator with polyfunctional active hydrogen molecules and a polymer chain of propylene oxide and ethylene oxide units, with a mean molecular weight of 3,500 + 200, placed in a reactor fitted with a stirrer, heater jacket, cooling coil and able to withstand pressure and vacuum. The reactor is first placed under vacuum, then heated to a temperature of 11 00C. Having reached that temperature, proceeding at the rate of 1 50 + 20 g/minute, a mixture of 1,650g of the same compound with a mean molecular weight of 3,000 + 200, 1,600 g of acrylonitrile, 340 g of styrene, 60 g of methylmethacrylate and 25 g of azobisisobutyronitrile. Pressure in the reactor rises slowly during the course of the reaction.Having completed the addition the temperature is maintained for 2 hours to ensure the reaction of eventual residual monomers. A vacuum of 14 mm of Hg is then applied for 4 hours. On completion of this process, the product is assessed, defining the acidity index, hydroxyl index and moisture content.

EXAMPLE 2 The same synthesis process as in example 1 is applied, with the exception of the addition of 1,600 g of acrylonitrile, 300 g of styrene, and 100 g of methylmethacrylate.

EXAMPLE 3 The same procedure as in examples 1 and 2 is applied, adding 1,600 g of acrylonitrile, 380 g of styrene and 20 g of methylmethacrylate.

Results obtained in defining the products obtained are as follows: Example 1 Example 2 Example 3 Hydroxyl index 38.27 38.27 38.46 Acidity index 0.088 0.063 0.082 Moisture content 0.080 0.096 0.092 EXAMPLE 4 The same procedure as in examples 1,2 and 3 is adopted. In this case, 5,350 g of polyhydroxylic compound are used, having a molecular weight of 3,0001 150, to which are added 4,150 g of prior polyol ether, 250 g of acrylonitrile, 245 g of styrene, 5 g of methylmethacrylate and 12.5 g of azobisisobutyronitrile.

EXAMPLE 5 As for example 4, but adding 3,650 g of polyol ether, 500 g of acrylonitrile, 490 g of styrene, 10 g of methyl methacrylate and 25 g of azo-bis-iso-butyronitrile.

EXAMPLE 6 Similar to examples 4 and 5, but adding 3,1 50 g of polyol ether, 750 of acrylonitrile, 735 g of styrene, 1 5 g of methylmethacrylate and 37.50 of azo-bis-iso-butyronitrile.

Results obtained in defining the 4 examples are as follows: Example 4 Example 5 Example 6 Example 7 Hydroxyl index 53.0 50.2 47.0 44.6 Acidity index 0.04 0.04 0.04 0.03 Moisture content 0.08 0.08 0.06 0.06 Products obtained from examples 1,2 and 3 were foamed according to formulations shown in Schedule 1.

The foams were rested for 24 hours, then physical properties as outlined in Schedule 1 were checked.

Product No. 2 was submitted to detailed investigation, proceeding with foaming according to Schedules 2 to 8, with relevant proportions of product and water in the formulations.

After settling for 24 hours, foams were assessed, and values are defined in Tables II to VI II.

Examples 4, 5, 6 and 7 were foamed according to the formulations in Schedule 9.

Foams were settled for 24 hours, then checked for physical properties as shown in Table IX.

SCHEDULE 1 Polyol I OH 48 Example 1.

Example 2.

Example 3.

Silicone Triethylenediamine Water Tin octoate (Index 105)TDI

For. 1 For. 2 For. 3 For. 4 For. 5 For. 6 For. 7 For. 8 For. 9 For. 10 100 90 80 70 90 80 70 90 80 70 - 10 20 30 - ~ ~ ~ ~ ~ - - - - 10 20 30 ~ ~ ~ - - - - - - - 10 20 30 1,10 1,10 1,10 1,10 1,10 1,10 1,10 1,10 1,10 1,10 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 4,00 4,00 | 4,00 4,00 4,00 4,00 4,00 4,00 4,00 4,00 0,23 0,23 0,23 0,23 0,23 0,23 0,23 0,23 0,23 0,23 48,85 48,83 48,76 48,60 48,83 48,76 48,60 48,83 48,76 48,60 TABLE II PROPERTY Tensile (kgf/mm) Elongation (%) compression 10% set 50% Tearing test (daN/cm) CLD EU BO 25% 52-1 Hardness 40% FORD 50% (Newtons) 65% Density (kg/cm )

For. 1 For. 2 For. 3 For. 4 For. 5 For. 6 For. 7 For. 8 For. 9 For. 10 0,912 1,350 1,320 1,570 1,200 1,220 1,180 1,150 1,290 1,250 239 211 258 242 250 263 232 206 234 235 2,70 4,94 4,17 2,89 2,20 4,20 4,58 1,72 1,62 2,97 3,60 11,0 12,95 10,90 5,00 10,71 15,00 3,79 9,80 9,66 0,606 0,850 0,790 0,862 0,681 0,660 0,737 0,701 0,815 0,812 14,65 15,94 17,66 20,35 17,72 18,29 18,53 19,79 20,44 17,87 16,96 18,78 19,96 23,82 22,02 21,19 22,35 24,20 22,09 19,95 20,19 21,07 23,79 28,13 25,50 25,01 26,98 27,78 26,27 22,07 28,94 36,04 39,39 47,88 43,31 42,42 46,07 46,94 44,75 40,28 25,85 24,81 25,60 25,60 24,80 25,40 24,60 25,00 25,00 26,30 SCHEDULE 2

For. 1 For. 2 For. 3 For. 4 For. 5 For. 6 For. 7 For. 8 For. 9 Polyol I OH 48 90 90 90 90 90 90 90 90 90 Example 2. 10 - - - - 10 10 - Commercial Polyol 1 - 10 - 10 - - - 10 Commercial Polyol 2 - - 10 - 10 - - - 10 Silicone 1,0 1,0 1,0 1,2 1,2 1,4 1,4 1,4 1,4 Triethylenediamine - - - - - 0,12 0,12 0,12 0,12 Polycat 12 0,12 0,12 0,12 0,25 0,26 - - - Water 3,1 3,1 3,1 4,00 4,00 4,00 4,95 4,95 4,95 Tin octoate 0,2 0,2 0,2 0,20 0,20 0,2 0,2 0,2 0,2 (Index 105) TDI 30,43 39,43 30,43 49,20 49,20 58,20 58,20 58,20 58,20 SCHEDULE 3

For. 10 For. 11 For. 12 For. 13 Polyol I OH 48 80 80 80 80 Example 2. 20 - - 20 Commercial Polyol 1 - 20 - Commercial Polyol 2 - - 20 Silicone 1,0 1,0 1,0 1,2 Triethylene diamine - - - Polycat 12 0,12 0,12 0,12 0,25 Water 3,1 3,1 3,1 4,00 Tin octoate 0,20 0,20 0,20 0,20 (Index 105) TDI 39,11 39,11 39,11 49,11 SCHEDULE 4 Polyol I OH 48 Example 2.

Commercial Polyol 1 Commercial Polyol 2 Silicone Triethylene diamine Polycat 12 Water Tin octoate (Index 105) TDI

For. 14 For. 15 For. 16 For. 17 For. 18 For. 19 For. 20 For. 21 80 80 80 80 80 70 70 70 - - 20 - - 30 - 20 - - 20 - - 30 - 20 - - 20 - - 20 1,2 1,2 1,4 1,4 1,4 1,0 1,0 1,0 - - 0,12 0,12 0,12 - - 0,25 0,25 - - - 0,12 0,12 0,12 4,00 4,00 4,95 4,95 4,95 3,1 3,1 3,1 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 48,74 49,31 57,90 57,90 57,90 38,78 38,78 38,78 SCHEDULE 5 Polyol I OH 48 Example 2.

Commercial Polyol 1 Commercial Polyol 2 Silicone Triethylene diamine Polycat 12 Water Tin octoate (Index 105) TDI

For. 22 For. 23 For. 24 For. 25 70 | 70 70 70 30 = - 30 - 30 - - - 30 1,2 1,2 1,2 1,4 - - - 0,12 0,25 0,25 0,25 4,00 4,00 4,00 4,95 0,20 0,20 0,20 0,20 47,92 47,92 47,92 57,55 SCHEDULE 6 Polyol I OH 48 Example 2.

Commercial Polyol 1 Commercial Polyol 2 Silicone Triethylene diamine Polycat 12 Water Tin octoate (Index 105)TDI

For. 26 For. 27 For. 28 For. 29 For. 30 70 70 100 100 100 30 - - - 30 1,4 1,4 1,0 1,2 1,4 0,12 0,12 - - 0,12 - - 0,12 0,25 4.95 4,95 3,1 4,00 4,96 0,20 0,20 0,20 0,20 0,20 57,55 57,55 39,76 49,80 58,52 SCHEDULE 7 Polyol I OH 48 Example 2.

Commercial Polyol 1 Silicone Solid Dobco Polycat 12 Water Tin Octoate 105 Index TDI

For. 31 For. 32 For. 33 For. 34 For. 35 For. 36 For. 37 For. 38 For. 39 For. 40 97,50 95,00 92,50 97,50 95.00 92,50 97,50 95.00 92,50 97,50 2,50 5,00 7,50 2,50 5,00 7,50 2,50 5,00 7,50 - - - - - - - - - - 2,5 1,0 1,0 1,0 1,2 1,2 1,2 1,4 1,4 1,4 7.0 - - - - - - 0,12 0,12 0,12 0,12 0,12 0,12 0,25 0,25 0,25 - - - 0,12 3,1 3,1 3,1 4,0 4,0 4,0 4,95 4,95 4,95 3,10 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 40,26 40,26 40,26 49,35 49,30 49,15 58,99 58,80 58,70 40,26 SCHEDULE 8 Polyol I OH 48 Example 2.

Commercial Polyol 1 Silicone Triethylene diamine Polycat 12 Water Tin Octoate (105 Index) TDI

For. 41 For. 42 For. 43 For. 44 For. 45 For. 46 For. 47 For. 48 95,00 92,50 97,50 95,00 92,50 97,50 95,00 92,50 5,00 7,50 2,50 5,00 7,50 8,00 5.00 7,50 1.00 1,00 1,20 1,20 1,20 1,40 1,40 1,40 - - - - - 0,12 0,12 0,12 0,12 0,12 0,25 0,25 0,25 - - - 3,10 | 3,10 4,00 4,00 4,00 4,95 4,95 4,95 0,20 0,20 0,20 0,20 0,20 0,20 0,20 0,20 40,26 40,26 49,35 49,30 49,15 58,80 58,80 58,70 TABLE lil PROPERTY Tensile (kgf/cm2) Elongation (%) Compression 10% set 50% Tearing str. (daN/cm) CLD EU BO 52 1 (25%) Hardness (40%) FORD (50%) (Newtons) (65%) Density (kg/cm3)

For. 1 For. 2 For. 3 For. 4 For. 5 For. 6 For. 7' For. 8 For. 9 1,375 1,429 1,324 1,344 1,341 1,178 1,500 1,220 1,290 233 229 242 264 -238 226 206 212 282 2,0 1,8 3,0 2,6 1,8 3,0 3,0 4,5 3,7 7,5 5,8 4,8 8,5 6,2 6,1 9,5 13,5 15,8 0,820 0,674 0,861 0,809 0,779 0,817 0,781 0,793 0,803 22,4 22,2 19,5 19,5 18,5 16,85 18,6 18,4 15,1 26,5 25,4 22,5 22,5 21,5 19,78 21,8 21,8 17,1 31,3 31,3 26,7 26,6 26,2 24,62 27,8 26,1 20,6 48,8 50,2 44,1 43,8 41,8 39,27 45,9 52,9 33,5 32,23 32,63 31,50 25,23 24,84 25,09 21,62 21,96 21,96 TABLE IV PROPERTY Tensile (kgf/cm2) Elongation (%) Compression 10% set 50% Tearing Str. (daN/cm) CLD EU BO 52 1 (25%) Hardness FORD 50% (Newtons) 65% Density (kg/m3)

For. 10 For.11 For. 12 For. 13 1,600 1,600 1,520 1,170 233 252 262 219 2,9 2,5 3,0 2,5 5,7 5,2 8,0 7,0 0,861 0,803 0,819 0,729 22,5 21,1 21,8 19,9 25,3 23,7 24,4 23,2 30,5 29,9 28,3 28,2 47,9 46,1 47,4 46,7 32,72 31,50 31,40 24,92 TABLE V -PROPERTY Tensile (kgf/cm2) Elongation (%) Compression 10% set 50% Tearing str. (daN/cm) CLD EU BO 52 1 (25%) Hardness (40%) FORD (50%) (Newtons) (65%) Density (kg/cm3)

For.14 For.15 For.16 For.17 For.18 For.19 For.20 For.21 1.264 1,347 1,510 1,728 1,484 1,740 1,434 1,600 223 216 184 205 182 200 265 205 1,7 2,3 4,4 4,2 2,2 2,5 3,2 2.9 6,0 7,6 7,9 13,7 6,6 5,9 6,7 5.9 0,688 0,800 0,797 0,864 | 0,720 0,978 0,940 0,852 20,6 | 20.1 18,4 20,2 15,9 21,4 24,5 21,3 24,4 23,5 20,9 23,3 18,2 24,3 27,5 24,4 28,4 28,7 24,7 28,3 21,4 28,5 32,5 28,8 47,13 47,7 43,5 45,1 37,0 48,5 53,2 46,9 25,24 24,95 21,54 22,38 20,10 31,91 31.28 32,07 TABLE VI

PROPERTY For. 22 For. 23 For. 24 For. 25 Tensile (kgf/cm) 1,389 1,126 1,108 1,610 Elongation (%) 251 204 182 243 Compression 10% 3,3 2,9 3,4 4,0 set 50% 8,3 7,1 7,6 10,9 Tearing Str. (daN/cm) 0,839 0,783 0,618 0,778 CLD EU BO 52 1 25% 19,8 20,8 17,0 19,8 Hardness 40% 23,1 24,1 20,7 23,6 FORD 50% 27,7 28,6 24,5 27,0 (Newtons) 65% 46,7 49,0 41,3 44,7 Density (kg/m ) 25,54 24,90 23,88 21,65 TABLE VII

PROPERTY For. 26 For. 27 For. 28 For. 29 For. 30 Tensile (kgf/cm) 1,290 1,300 1,500 0,972 1,072 Elongation (%) 226 206 270 264 220 Compression 10% 3,9 4,6 2,8 2,4 4,1 set 50% 10,8 11,0 6,2 6,9 11,0 Tearing Str. (daN/cm) 0,804 0,677 0,850 0,649 0,692 CLD EU BO 52 1 25% 17,2 17,3 18,7 17,1 16,7 Hardness 40% 20,5 19,4 21,5 19,1 18,0 FORD 50% 28,6 22,3 25,6 23,8 20,4 (Newtons) 65% 46,2 36,4 40,7 36,6 34,9 Density (kg/m ) 20,74 21,46 30,75 25,40 20,50 TABLE VIII PROPERTY Tensile (kgf/mm) Elongation (%) Compression 10% set 50% Tearing str. (daN/cm) CLD EU BO 52 1 (25%) hardness (40%) FORD (50%) (Newtons) (65%) Density (kg/cm )

For. 31 For. 32 For. 33 For. 34 For. 35 For. 36 For. 37 For. 38 For. 39 For. 40 1,369 1,437 1,369 0,950 0,928 1,179 1,058 1,078 1,054 1,253 267 225 248 210 176 251 229 217 186 237 2,4 2,3 2,8 2,6 2,3 3,2 3,7 5,1 4,7 2,7 6,1 6,8 6,5 7,4 6,9 8,0 8,6 11,6 14,5 6,4 0,825 0,866 0,826 0,537 0,650 0,776 0,744 0,722 0,680 0,946 20,8 22,0 22,5 19,5 18,4 18,6 17,2 15,6 17,1 21,0 24,0 25,5 25,7 22,6 20,8 21,4 19,7 17,7 19,5 24,3 28,2 31,3 30,6 26,7 25,2 25,7 24,6 20,6 22,6 29,6 46,2 49,2 49,2 43,6 41,0 42,4 42,1 34,7 37,3 50,0 32,45 32,53 32,67 26,12 25,93 26,17 21,65 21,01 21,02 32,04 TABLE IX PROPERTY Tensile (kgf/cm) Elongation (%) Compression 10% set 50% Tearing str. (daN/cm) CLD EU BO 52 1 (25%) Hardness (40%) FORD (50%) (Newtons) (65%) Density (kg/cm )

For. 41 For. 42 For. 43 For. 44 For. 45 For. 46 For. 47 For. 48 1,349 1,489 0,976 1,004 0,955 1,324 1,100 1,139 231 215 179 191 164 216 211 209 3,3 2,3 2,5 1,3 1,4 3,5 4,6 5,8 5,0 5,2 6,2 2,9 3,4 8,2 10,2 6,8 0,836 0,880 0,696 0,699 0,677 0,610 0,711 0,668 22,4 23,6 18,0 19,0 18,0 17,0 17,2 17,4 24,8 27,1 21,6 21,3 20,9 19,5 19,8 20,2 29,3 32,2 24,6 25,4 24,5 22,6 23,2 23,5 49,5 53,7 43,9 42,1 42,5 38,8 37,8 41,2 33,09 26,73 26,73 26,80 25,86 22,08 21,42 21,13 SCHEDULE 9 Polyol IOH 56.1 Example 4.

Example 5.

Example 6.

Example 7.

Tin octoate Dabco 33 LV NEM Water Silicone TDI

For. 1 For. 2 For. 3 For. 4 For. 5 For. 6 For. 7 For. 8 For. 9 For. 10 For. 11 For. 12 For. 13 100 100 100 100 100 100 100 100 100 100 100 100 100 - 10 15 20 - - - - - - - - - - - - 10 15 20 - - - - - - - - - - - - 10 15 20 - - - - - - - - - - - - 10 15 20 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,12 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,10 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 0,40 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 3,50 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 1,00 44,54 45,56 45,87 46,28 45,42 45,81 46,20 46,37 45,73 46,10 45,33 45,68 46,02 TABLE X PROPERTY Tensile (kgf/cm) Elongation (%) Compression 10% set 50% Tearing str. daN/cm CLD EU BO 52 1 20% Hardness 25% FORD 40% (Newtons) 50% Density kg/cm

For. 1 For. 2 For. 3 For. 4 For. 5 For. 6 For. 7 For. 8 For. 9 For. 10 For. 11 For. 12 For. 13 1,134 1,336 1,240 1,110 1,320 1,350 1,300 1,330 1,354 1,404 1,229 1,378 1,389 118 156 150 135 156 156 144 155 153 165 135 146 150 2,9 2,24 1,78 2,04 1,90 2,22 2,09 2,07 1,96 1,40 1,39 1,19 3,02 5,6 4,47 4,30 4,03 4,75 4,51 4,40 4,37 3,85 3,50 3,27 3,08 5,61 0,594 0,566 0,584 0,634 0,645 0,649 0,588 0,586 0,590 0,626 0,650 0,643 19,62 21,43 20,51 19,60 19,65 20,68 20,63 20,27 20,47 23,62 20,77 21,36 23,38 20,99 23,04 21,77 20,85 20,82 22,05 21,80 21,62 21,77 23,62 20,77 21,36 23,38 25,4 28,11 26,74 25,62 25,66 27,11 27,05 26,27 25,46 28,58 25,48 25,62 22,07 30,40 33,56 31,64 30,80 30,80 32,61 32,55 31,23 31,68 34,08 30,62 31,09 31,53 32,00 36,80 40,66 38,03 38,06 30,33 40,41 37,73 28,63 41,13 39,50 39,30 39,70

Claims (11)

1. A process for obtaining vinyl copolymer in a polyhydroxyl solvent, by reaction of a mixture of monomers containing acrylonitrile, styrene and methyl metacrylate, in the presence of a free radical catalyst wherein the polymerisation is carried out in a vacuum and with a slow increase in the pressure in a polyhydroxyl compound and with a monomer composition containing 7090% of acrylonitrile, 9-12% of styrene and 19% of vinyl monomer differing from the prior types, and preferably consisting of methylmethacrylate, the polymerisation being completed by heat treatment controlled according to the nature of the relevant catalyst and the viscosity which is required in the resulting product.

2. A process according to claim 1, wherein the polymerisation is effected in the absence of inert gas.

3. A process according to claim 1 or 2, wherein polymerisation is effected with an initial vacuum and a slow development of pressure generated automatically during the course of polymerisation.

4. A process according to claim 1 or 2, wherein the polyhydroxyl compound has an average molecular weight of 2 103 to 8.5 103.

5. A process according to claim 1, 2 or 3, wherein the mixture of vinyl monomers is used in an amount of 5% to 30% by weight on the basis of the combined weight of polyhydroxyl solvent and monomers.

6. A process according to claims, 1, 2, 3 or 4, wherein the mixture of vinyl monomers contains by weight 7O--90% de acrylonitrile, 21-9% of styrene and 9-1% of methylmethacrylate.

7. A process according to any one of claims 1 to 5, wherein said vinyl monomer differing from the prior types is methyl methacrylate.

8. A process according to claims 1, substantially as hereinbefore described in any one of Examples 1 to 7.

9. Vinyl copolymer in a polyhydroxyl solvent when obtained by a process as claimed in any preceding claim.

10. A polyurethane when produced using a vinyl copolymer in a polyhydroxyl solvent as claimed in claim 9.

11. A polyurethane as claimed in claim 10, substantially as hereinbefore described in the foregoing Formulations.