FR2591603A1 - PROCESS FOR OBTAINING VINYL COPOLYMERS OF A POLYHYDROXYL COMPOUND. - Google Patents

Abstract

The present invention relates to a process for obtaining vinyl copolymers of a polyhydroxylated compound, said vinyl copolymers being formed by a mixture containing from 90 to 20% of acrylonitrile, 80 to 5% by weight of styrene and 70 to 30% by weight of methyl methacrylate, the polyhydroxylated compound in which the copolymerization occurs comprises a polyoxyalkylenated product whose number average molecular mass, determined by assay of the terminal reactive groups is between 2.10 ** 3 and 8.5.10 ** 3; said polyhydroxy compound constitutes a proportion of the terminal mixture which is between 95 and 60% by weight; moreover, the copolymerization is carried out under pressure in order to avoid polymerizations in the gas phase. The products obtained are transformed into flexible polyurethane foam by adding an isocyanate, catalysts and additives, and these foams exhibit excellent hardness properties without adversely affecting the flexibility properties.

Description

2 5 9 1 603

-1 -

  PROCESS FOR OBTAINING COPIES; VINYL YMERES

OF A POLYHYDROXYL COMPOUND.

  The present invention relates to a method for obtaining

  vinyl copolymers of a polyhydroxy compound.

  Polyrnere denotes a large molecule constituted by the

  rJp.2ti! 'kn other or smaller simple ones, called monomers.

  Polymers are formed by two types of reaction, polycocensatlon and polyaddition. We will refer to the polymers obtained

by polyaddition.

  Polyaddition denotes a reaction in which the chain in formation is produced by an ion or by a substance with a single electron designated by free radical. The radical is generally formed

  by decomposition of a relatively unstable matter called initiator.

  Said free radical is capable of reacting to open the double bond of a

  vinyl monomer by adding thereto, with an electron remaining single.

  In a very short time, many monomers successively add to the growing chain. Finally, two free radicals react by

  canceling their reactivity and form one or more polymer molecules.

  To this type of reaction correspond vinyl polymers. These are subdivided into homopolymers and copolymers. The former are formed from a single monomer and, by way of representative examples, we can cite polyacrylonitrile, polystyrene, polymethyl methacrylate, etc. The others are formed from two or more monomers and, by way of examples, mention may be made of polyacrylonitrile estyrene, polyethylene vinyl acetate, polyacrylonitrile-butadenestyrene, etc. The present invention deals with synthesis and application of a

  type of polymer obtained by polyaddition, by a radical mechanism.

  Polyaddition reactions are divided into homogeneous and heterogeneous polymerizations. The first are those in which the initial reaction mixture is homogeneous and the others are those in which the mixture is not. Some homogeneous systems may become heterogeneous as polymerization continues due

  insolubility of the polymer in the reaction medium.

  Homogeneous polymerizations can be in bulk and in solution; -2heterogeneous in suspension and in emulsion. The present invention deals with

  homogeneous polymerizations in solution.

  Vinyl polymerization is an exothermic process which involves the transformation of n bonds into bond (e); the polymerization energy depends on the nature of the groups: neighbors of the carbons which bear the double bond, which p. u: ent faeciliir 1l rupture of said double bond by

  effects of indut an Jc deu e ju:, asc; (table 'i.

  Mcnornère; 1. Ethylene 2. Propylene 3. Isobutylene 4. Butene-1 5. Isoprene 6. Styrene 7. oC-m ethyl styrene 8. Vinyl chloride 9. Vinyl acetate 10. Acrylonitrile 11. Methyl methacrylate 12. Acrylate ethyl 13. Methyl acrylate 14. Acrylamide J. ie '

-CH -CHIT -

-CH2-CH (CH3) -

-CH 1- (CH)

2 3

-CH2-CH (C2H5) -

-CH2-C (CH3) = CH-CH2-

-CH2-CH (C6H 5-

-CH2-C (CH3) (C6H5) -

-CH2-CHCI-

-CH 2-CH (C2H 30) -

-CH2-CH (CN) -

-CH2C (CH3) (C H302)

-CH2-CH (C3H 502) -

-CH2-CHI (C2H302) -

-CH2-CH (CONH2) -

AHP, Kcal / mc} e.

  22.7, 5 12.3, 0 17.4 16.7 8.4 22.9 21.0 18.4 13.5 18.8 18.8 19.8 Solution polymerization avoids many disadvantages of mass polymerization. The solvent acts as a diluent and promotes the heat of polymerization, moreover, its presence by reducing the viscosity of the medium, allows easier agitation. Thermal control is much simpler with solution polymerization than, for example,

with bulk polymerization.

  The kinetic scheme of the radical polymerization is represented as follows: Initiation Propagation Kd x2

I ..... M. 2R

  Rx + xM Kp PxN -3- End Addition Px + Py Kt Px- Py Mutation Px + Py Kt Px- H + Py Transfer PzX + AH Ktr Pz - H + AX The flexibility of use of polymers obtained by solution polymerization is extreme. This is the reason why we thought of obtaining a type of these compounds which could be applied in a field which we studied and we used polyurethane polymers. These polymers 0 are obtained by reacting a compound with polyhydroxylated groups, and another with polyisocyanate groups. There is a correlation between the chemical structure of the starting compounds and the physical properties of the final compound. An analysis will be made of the following factors: a) the intermolecular forces also called "secondary chemical bonds", result from the formation of hydrogen bridges, dipole moments, polarizability and Van der Waals forces. These intermolecular forces tend to link the chains in a similar fashion to the primary chemical bonds, thereby increasing the tensile strength, shear strength, hardness and glass transition temperature, for example with polyacrylonitrile and polymethyl methacrylate; b) the rigidity of the chains comes mainly from rigid structures such as aromatic rings, for example, polystyrene. Logically, rigidity promotes hardness, tensile strength and reduces elasticity; c) the higher the crosslinking, the greater the hardness and

the lower the flexibility.

  From these parameters, it is possible to design one of the compounds, isocyanate or polyhydroxylated compound, making it possible to obtain polyurethanes adapted to our needs. Since the isocyanate is very reactive towards many compounds, such as humidity

  from the environment, it is preferable to use the polyhydroxy compound.

  The object exposed in the present invention is the obtaining of vinyl polymers by solution polymerization, using as solvent a polyhydroxylated compound, so as to obtain a reactive final composition, by the hydroxyl groups with respect to the isocyanate. and with a series of

  properties conferred by the vinyl polymer.

9 1 6 03

  -4- Compositions of this type have been developed and are described

  in previously published works and patents.

  Acrylonitrile polymers were originally used with various types of polyhydroxy compounds. The following patents can thus be cited:

US N 3,304,273,

GB NO 1.040.452,

BE N 643.340.

  Polyacrylonitrile styrene copolymers were then synthesized into polyhydroxy compounds described in the following patents:

CA NO 785.836,

BE N0 788.115,

DE N 1.152.536 / 1.152.537.

  In the applicant's case, three acrylonitrile-styrene and methyl methacrylate monomers were used; they were selected according to their chemical structure and their physical properties,

  as mentioned in the paragraph above.

  Polyacrylonitrile unites a strong polarity and a low volume of the -C-N group which results in a high intermolecular force. It also has high solubility, which gives high resistance

with organic solvents.

  Polystyrene has aromatic nuclei and therefore high rigidity as well as intense intermolecular forces. Its thermal conductivity is very low. It is inert in the presence of many

mineral reagents.

  Polymethyl methacrylate combines high rigidity and hardness properties as well as great resistance to aging. It is also very resistant to mineral reagents, with the exception of mineral acids. In view of what has been mentioned in these last three paragraphs, it has been thought to synthesize a copolymer comprising the three monomers in an appropriate proportion in order to obtain an optimum balance between the various properties. Said copolymer has been synthesized in solution, using a polyhydroxylated compound as solvent in order to provide hydroxyl groups reacting subsequently with functional isocyanates

multiple.

  The present invention describes the solution polymerization of a vinyl copolymer comprising 36 to 1% of acrylonitrile, 32 to 0.25% of styrene and 28 to 0.15% of methyl methacrylate, using a compound as solvent polyhydroxylated having a molecular weight ranging from

  2.10 to 8.5.10 and an initiator producing free radicals.

  The invention consists in carrying out the reaction under low pressure

  nitrogen to avoid gas phase polymerization.

  The polyhydroxy compounds used as solvents are products obtained by reacting, using a basic or acid catalyst, multifunction initiators with active hydrogens such as monoethylene glycol, monopropylene glycol, diethylene glycol, dipropylene glycol, 1,3- dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,2,6-hexanetriol, glycerol, trimethylol propane, pentaerythritol, sorbitol, sucrose, neopentylglycol, monoethanolamine, diethanolamine, '' triethanolamine, monoisopropanolamine, diisoopropanolamine, ethylenediamine, tolylenediamine, 1,10-dihydroxydecane, 1,2,4 trihydroxybutane, etc. The most widely used alkylene oxides are those of ethylene, propylene, styrene and butylene, either in the form of a homopolymer or a copolymer and the latter can be sequenced, random or

alternated.

  The basic catalysts used are sodium hydroxide, potassium hydroxide, sodium methylate, calcium oxide, alkali carbonates, alkali salts of fatty acids, dimethylamine, triethylamine, certain organometallic compounds, etc. . The most frequently used acid catalysts are: boron trifluoride, stannous chloride, titanium chloride, aluminum sulfate, benzoyl chloride, acetic anhydride, boric acid, sodium bisulfate, boron tribromide, etc. In the present invention, it is estimated that the most suitable polyhydroxy compounds are those which have a number-average molecular mass, characterized by the determination of the functional groups, of between 2.103 and 8.5.103, and particularly those which are between 3.103

and 6.5.103.

  The compounds described in the present invention are used to obtain cellular polyurethane compounds, which is why they must react with the polyisocyanates to present suitable catalysts. For the preparation of cellular polyurethane compositions, whether sequenced or of high resilience, it is essential to strictly control the stoichiometric ratios, that is to say to use only quantities in slight excess compared to the stoichiometric requirements of the polyisocyanate. organic. In other words, the reactants, the polyisocyanate and the polyhydroxylated compounds, are used in relative amounts such that the ratio between the equivalents of total NCO and the equivalents of total active H is of approx 0.8 to 1.5 , preferably from 0.9 to 1.2. This ratio is known as the isocyanate index and is generally expressed as a percentage of the stoichiometric amount of

  polyisocyanate necessary to react with total active H.

  The organic polyisocyanates which are used to produce the polyurethanes are organic compounds which contain at least two isocyanate groups. These compounds are very well known and among those which are most suitable, mention may be made of hydrocarbon diisocyanates (for example alkylene diisocyanates and arylene diisocyanates such as: - 1,2-diisocyanatoethane, - 1,4 -diisocyanatobutane, - 2,4diisocyanatotoluene, - 2,6-diisocyanatotolnylene, - 1,3diisocyanato-O-xylene, - 2,4-diisocyanato-1-chlorobenzene, - 2,5diisocyanato-1-nitrobenzene, - 4,4'-diphenylmethylene-diisocyanate, 3,3 'diphenylmethylene-diisocianate,

  - polymethylene-polyphenylene-diisocyanates.

  The catalysts useful for the production of polyurethanes according to the present invention include tertiary amines such as: - trimethylamine, - triethylamine, - tributylamine, - Nmethylmorpholine, - N-ethylmorpholine, - N-comorpholine, - N , N, N ', N'-tetramethyl-1,3-butanediamine,

259 1,603

  -7- - 1,4-diazobicylo (2,2,2) -octane, - pyridine oxide, - N, N, N ', N'-tetramethylenediamine, - N-methyl-N'- dimethylaminoethylpiperazine, - N, N-dimethylbenzylamine-bis- (N, Ndiethylaminoethyl) adipate, - N, N-diethylbenzylamine, - pentamethyldiethylene tetramine, - N, N-dimethyl-cyclohexylamine; - N, Ndimethylphenylethylamine, - 1,2-dimethylimidazole,

- 2-methylimidazole.

  Tertiary amines which contain active hydrogen atoms vis-à-vis isocyanate groups, such as triethanolamine; triisopropanolamine; N-methyldiethanolamine; ' N-ethyldiethanolamine; N, N-dimethylethanolamine; as well as their reaction products with alkylene oxides. It is also possible to envisage nitrogen bases such as tetraalkylammonium hydroxides; alkali hydroxides such as sodium hydroxide; alkylphenolates, such as phenolate

  sodium or alkaline alcoholates such as sodium methylate.

  The amine catalyst is present in the reaction mixture for producing the final urethane in an amount of between approximately 0.05 and 3 parts by weight of active catalyst, per 100 parts by weight of the polyhydroxylated reagent. Current practice is to include as an additional component of the reaction mixture a small amount of certain metal catalysts useful for promoting gelling of the mixture

forming the foam.

  The most common catalysts of this type are organometallic compounds, in particular organic tin compounds. Preferably, the tin (II) salts of the carboxylic acids such as tin (II) acetate; tin (II) octoate; tin (II) ethylhexoate; tin (II) laurate; tin (IV) compounds, for example dibutyl stannic oxide; stannic dichlorodibutyl; dibutyl stannic diacetate; dibutyl stannic dilaurate. Pure or mixed catalysts can be used and in general the amounts of metal cocatalysts which may be present in the reaction mixture are in the range of about 0.05

  2 parts by weight per 100 parts by weight of the polyhydroxylated reagent.

2S91603

  The formation of the cellular compound is obtained by the presence in the reaction mixture of variable quantities of an expanding or propelling agent. The basic agent is water, which results in the production of carbon dioxide "in situ" under the effect of the reaction with the isocyanate. Organic propellants are also used, such as, for example, acetone, ethyl acetate; substituted haloalkanes, such as methylene chloride; chloroform; vinylidene chloride; monofluorotrichloromethane; chlorodifluormethane; dichlorodifluoromethane and also butane, hexane, heptane or

diethyl ether.

  These agents vaporize as a result of the heat generation inherent in the reaction. The generally preferred method is to use only water, or a combination of water and a fluorinated hydrocarbon blowing agent. The amount of propellant used varies according to the density

and the desired hardness.

  For the production of cellular polyurethane compounds, stabilizers are also used which are selective with respect to the formation of a particular type of foam. The surfactant should maintain the original level of the foam once it has been formed. Foams produced with suitable surfactants undergo a

  minimum contraction or relaxation at the top.

  In accordance with the present invention, the stabilizing agents useful for the desired effects include the siloxanes of water-soluble polyolethers constituted by the union of a copolymer of ethylene oxide and of propylene oxide with a polydimethylsiloxane radical or, in general , for hydrolyzable block copolymers of polysiloxane-polyoxyalkylene, with those described in US Pat. Nos. 2,834. 748 and 2,917,480, as well as the non-hydrolyzable block copolymers of polyoxydial alkylene polysiloxane, such as those described in American patent n

3,505,377.

  Other examples of surface active additives and stabilizers as well as cell size regulators, reaction retarders, flame retardants, plasticizers, dyes and fillers as well as substances having fungistatic and bacteriostatic effects and multiple details on the use and mode of work of these additives, are given in 9-

  Kunststoff-Handbuch, tome VII edited by Vieweg and Hëchtlan, Carl Hanser-

Verlag, Munich 1965.

  The vinyl monomers used for the preparation of the compounds described in the present invention are used in a proportion of 5 to 40% by weight of the final product. The most suitable are those which have approximately 10 to 30% of a mixture of vinyl monomers relative to the total. The most suitable monomer mixtures according to the balance of properties are those which have approximately 90 to 20% of acrylonitrile, 80 to% by weight of styrene and 70 to 3% by weight of methyl methacrylate. The most commonly used free radical initiators are

  compounds such as azobis-isobutyro-nitrile; ..- peroxyneodecanoate

  cumyl, din-butyl peroxydicarbonate, dicyclohexyl peroxydihydrocarbonate, bis- (2-ethylhexyl) peroxydicarbonate, disopropyl peroxydicarbonate, t-butyl peroxynecarate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxypivalate bis (3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, terbutyl peroxybutyrate, terbutylperoxyisopropyl carbonate, dicumyl peroxide, etc. The quantities which are used are between approximately

  0.05 and 2.5% by weight of the product obtained.

  The choice of initiator depends on the graft which it is desired to obtain on the solvent as well as on the average lifetime of the initiator. The initiator's graft mainly depends on the amount of CH3 radicals that can be produced by decomposition, so for example azobisisobutyrolnitrile produces very little graft, while benzoyl peroxide produces a lot. The graft occurs in the tertiary carbon atoms existing in the oxypropylene chain of the polyhydroxy compound. The mean lifespan, for its part, is the time necessary for the concentration of the initiator to be reduced by half, to a

  determined temperature, which makes it possible to control the speed of the reaction.

  The reaction temperature is an important parameter for controlling the molecular weight of the vinyl polymer to be obtained and therefore the viscosity of the solution obtained. It is verified that at low temperatures, the molecular weight of the polymer increases greatly and consequently the viscosity produced is high. Conversely, when the temperature is high, the termination reaction is facilitated, so that the weight

2S91603

  -10- molecular increases little and therefore the viscosity is reduced. The temperature intervals in which one can work vary between and 1300 C, and if one wishes to obtain viscosities reduced between 100

and 130 C.

  Other elements which can intervene in these polymerizations are chain transfer agents which are substances which, in addition to the monomers to be polymerized, reduce their molecular weight as a result of a transfer reaction, by which a polymer chain in growth

  loses its activity by fixing a hydrogen atom of the transfer agent.

  The activity of chain transfer agents is very selective: for certain monomers, they behave like such agents, and for others they behave as retarding agents or inhibitors of

  polymerization, also their use should be carefully studied.

  The examples below illustrate the description of this

invention.

  To explain the terminology described in the experiments, the following keys were used: - Polyol 3500 denotes a polyester derived from glycerol with propylene oxide and ethylene oxide, whose average molecular mass

  in number determined by the technique of the hydroxyl number is 3500.

  - Polyol 5200 denotes a polyether derived from glycerol with propylene oxide and ethylene oxide, whose average molecular mass

  in number determined by the technique of the hydroxyl number is 5200.

- ACN denotes acrylonitrile.

- E denotes styrene.

  - MM denotes methyl methacrylate.

  - ABIN means' azobisisobutyronitrile.

  EXAMPLE: All the examples described below were carried out in a stirred stainless steel reactor, equipped with a heating bath, a cooling coil, and instruments suitable for controlling the pressure and the temperature. In all cases, the quantity of polyol described in each example was introduced into the reactor, the mixture is heated under a nitrogen atmosphere to the temperature indicated in the example and an N2 pressure of 2.9.105pa is applied. maintaining the same temperature and over a period of six hours, an initiating agent solution composed of polyol, of monomer and of the initiator is introduced,

259 1,603

- 1il -

  or mixtures of radical initiators.

  In all the cases examined, a transfer agent-inhibitor is also added beforehand to the polyol introduced into the reactor. Once the addition is complete, the post-reaction and evacuation are continued at the temperature at which the addition was carried out.

TABLE 1

  I 2 2 * 4 * s * 5 Polyol 3500 in the Polyol 3500 reactor in SI ACN in 51 Degree in Si MM dars SI Abin Tertiary butylbeneoate in SI

Peroxyisopropyl-

ctr.n t: de leret-

  buty: e in SI n- '> d'ylmercsptan de s reactew thylamine es ó réa: teur m pratlure se: tin en a C

Post temp4rlture

  r; action in a C Duration of po5-retetion Cen Hours

  1270 1270 1000 1540 1000 1000 1000 1000 1000

330 330 600 60 600 600 600 600 C00

200 200 200 200 200 160 120 g0

100 10 10 180 180 220 260 300

20 20 20 20 20 20 20 20

7 10 10 10 5 15 10 10 10

- '2 - - _ _

_ _ _ _. 5 _-

  120 i20 120 120 120 120 120. 120 Pt 4.

120 120 120 120 120 120 120 120

I 1 0.5 2 4 4 4 1 I

  Ternp: rature discharge in a C 120 120 120 120 120 120 120 120 120 120 120 Evacuation time, in hours 6 4 3,5 4 4 4 4 4 4 4 4

  Residual ACH ppm - - - - - - - - 2800 - -

  E residual ppm 104 269 84 194 3 - 2S 44 32 000 42 JS M1M residual ppm. . - - - 1500 Indie caddtAé, nrgXOlî 0.04 0.02 0.03 0.02 0.02 0.02 0.02 0, 0 Reali- 0.02 0.01 kd- & b-cerMN & 38.9 39.0 38.9 38.1 39.1 39.2 12.1 39.2 sation 39.1 39.2 Hwridt9i in P 0.02 0.02 0.01 0.04 0.03 0.01 0.01 0.02 no 0.01 0, 02 Y Viscosity i 25 * C Pa.s.13O 4t50 2100 1800 3460 1400 3520 2060 sl00 completed. 1900 J500

9 1 10I _ 12 13 14 1S

1000 1000

600 600

200

* 100

100

10

1000 1000 1000 1040

$ 600 00 s00 600

160 1I0 180

140 180 150

100 se60 20

10 10 10

t, to N

2 'o - - -

120 120 120 120 120

120 120 120 120 120

4 S 1 2

120 120 120

4 4 4 4

- 48 50 60

0.01 0.02 0.01 0.0

39.4 39.1 31.3 39, S

0.02 0.03 0.03 0.0

2500 3600 4200 1150

q) uli L (A

6- 7- '

TABLE 2

EXAMPLE

  Polyol 3500 in the reactor Polyol 3500 in Si ACN in Si Degree in Si MM in SI Abin T-butyl peroxybenzoate in Si T-butyl peroxyisopropylcarbonate in Si n-dodecylmercaptan in the Triethylamine reactor in the reactor km Addition temperature in * C Post-reaction temperature in * C Post-reaction time in hours Evacuation temperature in * C Evacuation time in hours Reduced ACS ppm E residual residue ppm Residual MM ppm Acidity index, mg KOH / g Hydroxyl index mg KOH / g Humidity% by weight Viscosity i 25 'C Pa, s.1 û3

16 _ 17 18 19 20 21 22 73 24 25

  1270 1000 1540 1000 1000 1000 1000 1000 1000 1000

  330 600 60 600 600 600 600 600 600 600

200 200 200 200 200 200 200 190 180

180 180 180 180 100 180 180 190 200

00 20 20 20 20 20 20 20 20 20

10 10 7.5 7.5 5 2.5 2.5 $ 2.5 10

- - 7.5 7.5 S 2, s 2.5

- I

0.5 1 '

120 120 120 120 120 120 120 120

120 120 120 120 120 120 120 120

I I] 3 3 3 3 3 6

120 120 120 "120 120 120 120 120

4 4 6 4 4 4 4 4 4 4

- - 300 684 - -

32 40 215 122 195 710 31 -

  0.02 0.03 0.02 0.02 0.03 0.02i 0.02 0.01 0.02 0.02

  26.2 26.3 26.4 26.2 26.2 26.3 .. 26.3 26.4 26.3 26.2

  0.02 0.03 0.02 0.02 0.01 0.02 0.01 0.02 0.02 0.02

  3800 2540 2960 30256; 400 * 000 6200 2646 3450 2417

c. * CO iN Ln f0 C, (A -14 -

TABLE 3

EXAMPLE

  Polyol 3500 in the reactor 1000 1000 1000 Polyol 3500 in SI 400 400 400 ACN in SI 480 480 480 Degree in SI 100 100 100 MM in SI 20 20.20 Abin 10 5 15 Peroxybenzoate

of tert-butyl in SI - - -

Peroxyisopropylcarbonate

of tert-butyl in SI - - -

n-dodecylmercaptan

in the reactor - - -

  Triethylamine in the reactor - - -

  Addition temperature in C 120 120 120 Post-reaction temperature in C 120 120 120 Post-reaction time in hours 2 1 1 Evacuation temperature in C 120 120 120 Evacuation time in hours 5 5 - 4

Residual ACN ppm - - -

E residual ppm

Residual MM ppm - - -

  Acidity index, mg KOH / g 0.02 0.05 0.02 Hydroxyl index mg KOH / g 34, 5 34.8 34.7 Humidity% by weight 0.02 0.03 0.03 Viscosity at 25 C, Pa.s.103 1760 4850 2110 -15- To illustrate the most important of the physical properties obtained with the foams prepared with these polyol ethers, a series of tests is described below, as shown in the following tables:

TABLE I

Formula 1 2 3 4

Poliol 3500 100 - - -

Example 2 - 100 -

Example 3 - - 100 -

  Example 4 - - - 100 Water 4.85 4.85 4.85 4.85 Dabco 33 LV 0.36 0.36 0.36 0.36 Silicone SC 240 1.30 1.30 1.30 1.30 Octoate tin 0.25 0.25 0.25 0.25 TDI (index 106) 58.56 57.09 57.09 57.09

TABLE II

Formula 5 6 7 8

Poliol 3500 100 - - -

Example 2 - 100 -

Example 3 - - 100 -

  Example 4 - - - 100 Water 3.95 3.95 3.95 3.95 Dabco WT 0.66 0.66 0.66 AT 0.66

D.M.A.E. 0.20 0.20 0.20 0.20 Silicone SC 240 1.1 1.1 1.1 1.1 Tin octoate 0.28 0.28 0.28 0.28 TDI

  (index 110) 51.25 49.63 49.63 49.63 Poliol 3500 formula

Example 2

Example 3

Example 4

Dabco WT Water

D.M.A.E.

  Silicone SC 240 TDI Tin Octoate (Index 110) -16 -

TABLE III

  3.1 0.05 0.15 1.00 0.26, 33 3.1 0.05 0.15 1.00 0.26, 30 The foams obtained according to Tables I, II and III were left for 24 hours and the physical tests described in Tables IV, V and VI

* were then carried out.

TABLE IV

  Dynamic fatigue H Constant deformation Loss of hardness (%)%%%%

- 2.82

- 34.00

- 32.7

- 28.80

- 25.30

- 3.23

- 33.81

- 33.03

- 32.42

- 23.69

- 3.41

- 33.95

- 34.30

- 33.33

- 28.08

- 2.66

- 34.90

- 34.02

- 31.12

- 24.52

  Rdstanceàla 35% 30.64 34.45 34.45 37.39 compression 40% 35.00 39.85 40, 22 43.41 Ford4 CICLO-70% 50% 40.71 48.07 48.18 49.05 Newtons 65% 69.35 80.44 77.99 82.04

_ 3

  Density kg / m 29.11 29.92 29.75 29.85 Traction 'Pa.10-5 1.257 1.259 1.258 1.259 Elongation (%) 138 128 130 130 Stance at 25% 19.88 23.25 23.30 25.50 penetration 65% 36.65 42.25 43.00 43.50 Pa. 1 0-5 SAG 1,809 1.782 1, 1 0 1.668 Deformation 50% 3.33 3.09 3.07 3.08 Retentive 75% 4.13 3.05 3.05 3.05 Resilience% 32 29 30 30 Cisaifment, Pa. 105 0.417 0.385 0.418 0.399 3.1 0.05 0.15 1.00 0.26, 30 3.1 0.05 0 .15 1.00 0.26

: 40.30

g * -

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-17 -

TABLE V

  Fatiguedynamniqe H - 4.34 - 7.09 - 7.10 - 7.06 Deformation 25% - 34.26 41.27 - 41.50 - 41.91 Constant 40% - 34.14 - 38.61 - 38, 70 - 38.81 Hardness loss 50% - 32.76 - 34.88 - 34.65 - 34.72

  (%) 60% - 24.81 - 17.80 - 17.75 - 17.62

  Rstaceà la 35% 16.67 38.74 38.62 38.81 compression 40% 19.62 46.59 46, 62 46.65

  KMD4 CYCIO-06 50% 22.89 53.95 53.94 53.91

  Newtons 65% 39.09 91.39 91.26 91.31 Density kg / m3 25.46 25.07 25.12 25.09 Traction Pa. 10-5 0.877 1.128 1.126 1.130

Elongation (%) - - - -

  Relsta àa 25% 13.75 24.50 24.39 24.46 penetration 65% 24.80 48.50 48.44 48.51 Pa.105 SAG 1,773 1,942 1,948 1,945 Deformation 50% 2.51 5.24 5, 23 5.27 Remanent 75% 3.62 8.18 8.15 8.21 Resilience% 32 22 23 23 Targeting Pa. 105 0.477 0.340 0.341 0.339 -18-

TABLE VI

9 10 11 12

  Fatguoeynamice H - 6.20 - 11.19 - 11.20 - 11.17 Deformation 25% - 36.48 49.24 - 49.15 - 49.20 Constant 40% -35.57 - 42.73 - 42, 92 - 42.80 Loss of hardness 50% - 32.94 - 42.54 - 42.65 - 42.25

  (%) 60% - 30.73 - 34.99 - 34.16 - 34.09

  Rdstanoeà] a 35% 18.79 32.21 32.10 32.06 compression. 40% 23.09 40.38 40.62 40.51

  K140 .CO 50% 27.30 49.37 49.53 49.48

  Newtons 65% 46.59 85.62 85.70 85.66 Density kg / m3 22.25 21.43 21.50 21, 45 Traction Pa. 105 0.995 1.036 1.023 1.011 Elongation (%) 186.20 118.80 119 .00 - 118.50 R'stanoeàla 25% 12.50 21.50 21.31 21.12 penetration 65% 24.10 39.00 39.22 39.31 Pa.105 SAG 1.891 1.779 1.805 1.825 Deformation 50% 4 , 00 11.17 11.20 11.10 Remanent 75% 6.68 24.21 24.30 24.22 Resilience% 34 23 24 24 Shear. Pa. 105 0.442 0.413 0.407 0.410

- 19 -

TABLE VII

  Formulation 1 2 3 4 5 Poliol 5200 100 50 50 50 50

Example 16 - 50 - - -

Example 17 - - 50 - -

Example 18 - - - 50 -

  Example 25 - - - - 50 Water 2.7 2.7 2.7 2.7 2.7 Diet * anne 1.0 1.0 1.0 1.0 1.0 Glycerol 2.0 2.0 2, 0 2.0 2.0 Dabco 33 LV 0.5 0.5 0.5 0.5 0.5 Niax A. 107 0.2 0.2 0.2 0.2 0.2 Silicone SH207 0.5 0, 5 0.5 0.5 0.5

  TDI (I: 103) 42.2 41.7 41.7 41.7 41.7

  The foams obtained according to Table VII were left to stand for a while.

  for 24 hours and then the physical tests described in Table VIII were carried out.

TABLE VIII

1 2 3 4 5

Tired

dynamic H - 1.28 - -

D ta1ion25% - 13.16 - - - -

Cartante 40% - 7.44 - -

Loss of

hardness 50% - 7.05 -

(%) 60% -10.58 - - - -

  R1sance35% 13.00 27.32 27.46 27.51 27.95

and the

  pressure 40% 16.42 35.10 35.31 34.99 35.80

FORD 4

  CYCID% 650% 20.84 44.50 44.63 44.20 45.12

  Newtor / cm 65% 36.04 77.85 77.98 77.99 79.94 Density! N3 42.24 42.58 42.60 42.50 42.74 TractionPa.1l-5 0.754 AMogement (% 6) 85 Resistance 25% 8.00 at p & ent 65% -20.80 Pa. 105 $ aG 2,550 DImt * n 50% 2.27

9m -

Resistance% -

  C (silently Pl10 '0.155 1.718 18.73 51.00 2.671 3.47 1.732 18.50, 80 2.693 3.52 1.727 18.59, 90 2.685 3.42 1.563 18.30 49.20 2.637 3.23

0.234 0.242 0.245 0.240

  Tables IV, V, VI and VIII demonstrate that a general improvement in the properties of the foams is obtained by using the polyol ethers described in the present invention instead of part or all of the conventional polyol ether, by varying the polyol ethers with respect to the content of monomers, the composition of the monomers,

  the initiator and the reaction conditions.

- 21 -

Claims (4)

  1) Process for the preparation of vinyl copolymers in a polyhydroxylated compound, having a number average molecular weight of between 2.103 and 8.5.103, by reacting a mixture of monomers containing acrylonitrile, styrene and methacrylate methyl, in the presence of a radical initiator, characterized in that said polymerization is carried out under pressure in a polyhydroxylated compound and with a monomer composition containing from 90 to 20% of acrylonitrile, 80 to 5% of styrene and 70 to 3% of a vinyl monomer different from the previous ones, and preferably consisting of methyl methacrylate, by carrying out the polymerization by heat treatment adjusted according to the nature   of said initiator and of the viscosity which is desired for the product obtained.   2) Process for the preparation of vinyl copolymers in a polyhydroxylated compound according to claim 1, characterized in that   the polymerization is carried out in the presence of an inert gas.   3) Process for the preparation of vinyl copolymers in a   polyhydroxy compound according to the preceding claims, characterized   in that the polymerization is carried out under higher pressure at atmospheric pressure.   4) Process for the preparation of vinyl copolymers in a   polyhydroxy compound according to Claims 1, 2 and 3, characterized in   that the mixture of vinyl monomers is used in a proportion of 5 to 40% by weight, based on the combined weight of the polyhydroxylated solvent and monomers.   ) Process for the preparation of vinyl copolymers in a   polyhydroxy compound according to Claims 1, 2 and 3, characterized in   that the mixture of vinyl monomers contains 90 to 20% by weight of acrylonitrile, 80 to 5% by weight of styrene and 70 to 3% by weight of methyl methacrylate.