DE3111266A1 - METHOD FOR PRODUCING REACTIVE LIQUID POLYMERISATS WITH FINAL VINYL GROUPS - Google Patents

Description

Process for the production of reactive liquid polymers with terminal vinyl groups

The reactive liquid polymers with terminal vinyl groups (vinyl terminated reactive liquid polymers or vinyl-terminated reactive liquid polymers, hereinafter referred to as "VTRLP" for short.) are Commercial products that can be hardened or vulcanized to solid elastomers. They are mainly used in

Coatings,

Sealing and casting compounds, investment compounds, as impact-resistant making agents for unsaturated polyester resins as well as in printing inks that use UV light or electron beams curable are used.

U.S. Patents 3,910,992 and 4,129,713 describe a large-scale one Process for producing VTRLP by addition reaction of a terminal carboxyl group reactive liquid polymer (carboxyl terminated reactive liquid polymer or carboxy1-terminated reactive liquid polymer, hereinafter referred to for short as "CTRLP") with glycidyl acrylate in the manner shown below:

0 0 0 0 0 OH 0

HOC -— P — COH + 2CH ₂ CHCH ₂ OCCH = CH ₂ - ^ P ^ f-COCH ₂ CHCH ₂ OCCH = CH ₂ ) ₂ This reaction is carried out at an elevated temperature of about to 150 ° C for a period of 10 to 20 Hours performed. This polymeric reaction product contains an extremely reactive functional group with terminal vinyl groups, which is easily polymerizable at elevated temperature. Since premature polymerization of the terminal vinyl group is undesirable, attempts have been made to carry out this reaction at a lower temperature with other reactants.

The invention relates to new reactive ones

liquid polymers with terminal vinyl groups (VTRLP) and a process for their preparation by a coupling reaction between an isocyanate, a Alcohol containing vinyl groups and a liquid polymer containing terminal hydroxyl groups (hydroxyl terminated liquid polymer or hydroxyl terminated liquid polymer, hereinafter referred to as "HTRLP" for short).

In detail, the process according to the invention consists of the steps of converting an HTRLP, an unsaturated one Alcohol and a diisocyanate at a temperature ranging from about room temperature to about 70 ° C.

The new VTRLP are made according to the one-step or two-step process by reacting a diisocyanate, an oc, ß-ethylenically unsaturated hydroxyl compound and a liquid polymer with terminal hydroxyl groups. The new VTRLP have molecular weights from about 1000 to 20,000, determined with a Mechrolab vapor pressure osmometer. Your bulk viscosity (bulk viscosity) is about 500 to 8,000,000 mPas, measured at 27 ° C with a Brookfield viscometer, Model LVT, with spindle no. 4. Of the new polymers, preference is given to those with a bulk viscosity from about 5000 to 2,000,000 mPas, in particular from about 10,000 to 1,000,000 mPas at 27 ° C. These polymers have Hydroxy1 equivalent weights of about 200 to 10,000.

In the two-stage coupling reaction of an HTRLP, a diisocyanate and an alcohol containing vinyl groups first the formation of an adduct takes place by reaction of the alcohol and the diisocyanate and then the Reaction between the adduct and the HTRLP. The two-step process is shown below:

R.
CH ₂ = CR-OH + O = C = NRN = C = O

I Il

CH ₂ = CR-O-C-NH-RN = C = O adduct

2 adduct + HO — P — OH

O ν ORP - (- OC-NH-R-NH-CORC = CH ₂ ) _

In the one-step process, the reaction takes place between the three reactants, as follows shown:

R.
2 CH ₂ = CR-OH + 2 O = C = NRN = C = O + OH-P-OH

0 ν

0 R 10 P — f-0-C-NH-R-NH-CORC = CH ₀ )

The new VTRLP can be used for two-stage or single-stage Process with or without a solvent can be produced. As shown above, the two-step process the alcohol is reacted with a diisocyanate to form an adduct which, with an HTRLP, results in the end product is implemented. The two-step process, when carried out without '' solvents, is harder to perform. Although the formation of the adduct is easily achieved, the second stage, i.e. the reaction of the adduct with the HTRLP due to the resulting high viscosity, which inhibits stirring and affects the quality of the end product, complicated. By using a solvent this can Problem to be solved.

In the one-step process, the reactants become put into a reactor in the following order:

HTRLP, vinyl group containing alcohol and diisocyanate. Preferably, the reactive liquid polymer a solvent is added before the remaining reactants are added. The viscosity of the VTRLP from the one-step process is usually higher than that of the VTRLP from the two-step process. A decrease in viscosity can be achieved by reducing the amount of vinyl group-containing alcohol relatively is increased to the diisocyanate. A lower viscosity of the VTRLP obtained can also be achieved by using HRTLP of lower viscosity can be achieved.

In the new one-stage and two-stage process, about 1 mole of alcohol containing vinyl groups is reacted with 1 mole of diisocyanate and 1/2 mole of HTRLP. To reduce the viscosity of the VTRLP obtained, as mentioned above, the molar ratio of alcohol to diisocyanate (OH / NCO) should be 1: 1 to slightly above this value, preferably to 1.5 moles of alcohol per mole of diisocyanate, in particular from 1.05 to 1.3 moles of alcohol per mole of diisocyanate. Although the rate of reaction is increased at higher temperature, the optimum temperature is for this process is in a range of less than 0 ⁰ C to 150 ° C, preferably in the range of room temperature of about 20 ° C to about 70 ° C.

The stability of the VTRLP depends on the stability of the vinyl groups and the unreacted isocyanate groups away. The vinyl groups can be inhibited by free radical-forming inhibitors, e.g. hydroquinone, benzoquinone, catechin, Toluhydroquinone, methyl ether of hydroquinone, trinitrobenzene, picric acid and phenothiazine, are stabilized, while the stability problem with the unreacted isocyanate groups by largely lowering their Proportion can be solved. This can be done by reacting residual isocyanate groups with materials such as Methanol, p-toluenesulfonic acid, ethylene glycol and triethanolamine can be achieved. Side reactions of the not

Any remaining isocyanate groups must be excluded in order to avoid gel formation of the VTRLP in a few hours. The concentration of the remaining isocyanate can be determined by the infrared spectrum of the ratio of the isocyanate group absorbance (A _n Q ₀ ) ^ ^ei

2260 cm for the cyano group extinction (A. ™) at 2240 cm ". The cyano groups come from the acrylonitrile and / or the free radical initiator. The lower this ratio, the more stable the product. For example, the product had of Example 8 an A _{n Q} / A _CN ratio of about 0.06, and its stability after storage for one month at room temperature and at an elevated temperature of about 60 ^° C. When the high content of residual isocyanate was lowered or turned off the stability of these products is significantly improved.

Although the process according to the invention can be carried out without a solvent, the reaction will preferably carried out in the presence of a solvent for the reactants. The amount of solvent can vary widely as a diluent to facilitate the physical aspects of the Handling and stirring of the reactants is added. If a solvent is used, its amount may be 20 to 400 parts by weight per 100 parts of VTRLP, preferably 50 to 150 parts. When used of a solvent, it should not contain any groups that react with the isocyanate groups or would interfere with the response in any way. So the solvent should not have hydroxyl groups, carboxyl groups or contain amine groups which could interfere with these reactions. This will make the suitable solvents for esters, ethers, hydrocarbons and similar solvents that are non-reactive, containing non-functional groups with respect to the isocyanate group.

Examples of polymerizable solvents that are hot These methods can be used are alkyl acrylates and methacrylates with 1 to 12 carbon atoms in the alkyl radical, styrene, alkylstyrene with 1 to 6 carbon atoms in the Alkyl radical, halogen and haloalkyl styrene with 1 to 6 carbon atoms in the alkyl radical, divinylbenzene, cyclohexyl acrylate and methacrylate, acrylonitrile, vinylidene chloride, vinyl acetate, Vinyl stearate, vinyl toluene, hexanediol diacrylate and dimethacrylate, polyethylene glycol diacrylate, vinyl propionate, Tetrahydrofurfuryl methacrylate, diethylene and triethylene glycol diacrylate, Diallyl fumarate, 1,3-butylene glycol diacrylate and dimethacrylate, trimethylol propane triacrylate and neopentyl glycol diacrylate. Non-polymerizable Solvents can also be used. Examples of such solvents are benzene, toluene, xylene, Dioxane, methyl ethyl ketone, ethyl acetate and ethylbenzene. Preferred solvents include styrene. Mixtures of styrene are further preferred solvents and methyl methacrylate and mixtures of styrene and

20 to name divinylbenzene.

As will be shown below, there are a wide variety of HTRLPs, all of which react with an alcohol containing vinyl groups and a diisocyanate can be used to produce VTRLP.

The production of HTRLP can take place, for example, by post-reaction of CTRLP, by free radicals Polymerization of monomers using initiators containing hydroxyl groups, by solution polymerization using lithium catalysts or organometallic catalysts and post-reaction of the Reaction product to form the hydroxyl groups Polymerization of a vinyl group-containing monomer with a hydroxyl group-containing trisulfide and / or Disulfide. Examples are HTRLP that run through Addition reaction between ethylene oxide and a CTRLP can be produced. The CTRLP can for their part through

free radical polymerization using Carboxyl group-containing initiators and / or modifying agents can be prepared as in U.S. Patent 3,285,949 and in DE-PS 1,150,205. The CTRLP can also be produced by producing polymers by solution polymerization using lithium catalysts or organometallic catalysts and Post-treatment of the polymers to form carboxyl groups can be prepared, as in US Pat. No. 3,135,716 and 3,431,235. Specific examples of HTRLP that are used with the vinyl group-containing alcohol and a Diisocyanate are reacted to form VTRLP, the butadiene-acrylonitrile copolymers containing terminal hydroxyl groups, which contain about 20% acrylonitrile and about 80% butadiene, terminal hydroxyl groups containing butadiene-acrylonitrile-hydroxyethyl acrylate copolymers, which is about 18% acrylonitrile, about 80% butadiene and up to a few percent hydroxyethyl acrylate containing terminal hydroxyl groups

20 butadiene-styrene copolymers, which are about 70%

Contains butadiene and about 30% styrene, polyepichlorohydrin with terminal hydroxyl groups, polybutadiene with terminal hydroxyl groups and butadiene-alkyl acrylate copolymers with terminal hydroxyl groups.

U.S. Patent 2,844,632 describes the preparation of HTRLP from bis (hydroxyalkylnaphthyl) disulfide by reacting a chlorosulfonylnaphthylacetic acid in the presence of Lithiumaluminiuirihydrid as a catalyst. U.S. Patent 3,551,471 describes the preparation of HTRLP by reacting CTRLP with ethylene oxide in the presence of a tertiary amine as a catalyst. Brookfield viscosity this HTRLP is up to about 50,000 to 80,000 mPas at 27 ° C. US Pat. No. 3,135,716 describes solution polymerization a vinyl compound in the presence of an organometallic catalyst and subsequent post-reaction of the product to replace the metal ions with hydroxyl groups and form HTRLP. The US PS

3 431 2 35 describes a reaction of a polydiene resin, e.g. 1,2-polybutadiene with terminal hydroxyl groups, with an organic chain extender, e.g. toluene-2,4-diisocyanate, in the presence of a free radical initiator. The reaction product is a stable one elastomeric material that can be hardened to a hard material at elevated temperature, which is mainly contains crosslinked, linearly elongated chains of fused cyclohexane groups through the chain-lengthening groups are connected to one another.

U.S. Patent 3,669,153 describes the preparation of HTRLP by reacting a CTRLP with a diol in the presence an acid catalyst. Specifically, the CTRLP of butadiene and polyalkyl acrylate becomes 5 to 10 times Excess of a difunctional hydroxy compound, the

Containing 3 to 6 carbon atoms, reacted in the presence of an effective amount of an acid catalyst. U.S. Pat

4,120,766 is directed to HTRLP prepared by polymerizing a vinyl monomer with a hydroxyl group containing Disulfide can be produced in the presence of UV light. These HTRLP have viscosities in the range of 500 to 2,500,000 mPas at 27 ° C and Hydroxy1 equivalent weights in the range of 200 to 10,000.

Monohydroxy compounds, the ethylenic compounds, are suitable as hydroxyl compounds for the production of VTRLP Contain double bonds and are free of substituents that are reactive with an isocyanate group. The hydroxyl group can be on any carbon atom of the alkyl radical, although it is preferably on terminal carbon atom from the ethylenic double bond. In particular, are suitable as Monohydroxyl compounds containing alcohols, vinyl groups, which are derived from hydroxyalkyl esters of unsaturated acids, Hydroxyl group-containing alkenes and vinylaromatisehen Alcohols are selected. The hydroxyalkyl esters

of unsaturated acids are preferably monohydroxy compounds with 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms in the alkyl radical. One or more carbon atoms in the Alkyl radicals can contain substituents derived from halogens, Nitrate, carbonate, substituted or unsubstituted alkyl radicals with 1 to 4 carbon atoms, alkoxy, alkenoxy and substituted and unsubstituted phenoxy groups are selected. Examples of such substituents are Acryloxy, methacryloxy, allyloxy, butoxy, methoxy, ethoxy, propyl, methyl, butyl radicals and methacrylate-alkylene or acrylate alkylene radicals with 1 to 4 carbon atoms in the alkylene part, for example in pentaerythritol triacrylate. The unsaturated acids from which the esters are derived contain 2 to 8 carbon atoms and include aliphatic ones and aromatic acids such as acrylic acid, methacrylic acid, cinnamic acid and crotonic acid.

Monohydroxy compounds containing vinyl groups Also suitable are alkenes with 1 to 12 carbon atoms, preferably 1-alkenes with 2 to 8 carbon atoms, the Hydroxyl group on the terminal carbon atoms.

Containing another group of suitable vinyl groups Monohydroxy compounds form the vinyl aromatic alcohols of the formula

in which R and X individually from hydrogen, halogens and Alkyl radicals having 1 to 4 carbon atoms are selected and η is a number from 0 to 12, preferably from 0 to 4. To to four radicals X can be on the aromatic ring.

In a preferred embodiment, suitable Hydroxy compounds from substituted and unsubstituted monohydroxyalkyl acrylates and methacrylates with 1 to 12 carbon atoms, preferably 2 to 4 carbon atoms in the alkyl radical

selected. Specific examples of suitable hydroxyl compounds for the preparation of VTRLP are 1-hydroxyethyl acrylate and methacrylate, hydroxypropyl and hydroxybutyl acrylates and methacrylates, 1-methacryloxydodecanol-2, 2-hydroxyethyl acrylate and methacrylate 3-acryloxy-2-hydroxypropyl methacrylate, 3-methacryloxy-2-hydroxypropyl methacrylate, 3-crotonoxy-2-hydroxypropyl acrylate, S-acryloxy ^ -hydroxypropylcinnamate, 3-allyloxy-2-hydropropyl acrylate, 2-hydroxybutyl acrylate and methacrylate, 4-hydroxy-2-methylbutyl acrylate, 4-hydroxyoctyl acrylate, Pentaerythritol triacrylate, 8-hydroxyoctyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- (o-chlorophenoxy) propyl acrylate, 3-chloro-2-hydroxypropyl acrylate and methacrylate, hydroxymethyl acrylate and methacrylate,

15 allyl alcohol, 4-hydroxylbutene-1, vinylphenols and Vinyl benzyl alcohol.

Suitable isocyanates include the aliphatic and cycloaliphatic and aromatic diisocyanates and polyisocyanates, preferably the diisocyanates. Examples suitable diisocyanates are 4,4'-methylene-bis (phenyl isocyanate), Toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, Naphthalene-1,5-diisocyanate, methylene diisocyanate, hexamethylene diisocyanate, Pentamethylene diisocyanate, cyclohexyl-2,4-diisocyanate, 4,4'-methylene-bis (cyclohexyl diisocyanate), Cyclohexylene-1,4-diisocyanate, butylbenzene-2,4-diisocyanate, Dodecylbenzene-2,4-diisocyanate, benzofuran-2,6-diisocyanate, Naphthalene-1,8-diisocyanate, fluorene-2,5-diisocyanate, Anthracene-1,4-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 2,4-diisocyanatostilbene, 4,4 "-diisocyanatodibenzyl, anthracene-9,10-diisocyanate, 4,6-dimethylphenylene-1,3-diisocyanate, benzidine diisocyanate, 4,4'-diisocyanatodiphenyl ether, 2,4-dimethylphenylene-1,3-diisocyanate, 2,4'-diisocyanatodiphenyl ether, 4-ethoxyphenylene-1,3-diisocyanate, 4-chlorophenylene-1,3-diisocyanate, Cumene-2,4-diisocyanate, naphthalene-1,5-diisocyanate and 3-1socyanatmethy1-3,5,5-trimethylcyclohexyl isocyanate.

In the following examples preferred embodiments of the method according to the invention for preparation described by VTRLP by reacting HTRLP with a diisocyanate and a hydroxyalkyl acrylate.

5 Example 1

This example describes the production of a VTRLP by a two-stage bulk polymerization reaction of toluene-2,4-diisocyanate (TDI) with 2-hydroxyethyl acrylate and then with HTRLP.

43.5 g (0.25 moles) of the toluene-2,4-diisocyanate were dropwise to a mixture of 29.0 g (0.25 mol) of 2-hydroxyethyl acrylate (HEA) and 0.03 g of phenothiazine as Stirring stabilizer added within 15 minutes at 40 ° C in dry air. After the addition of the Mixture, the temperature was raised to 65 ° C and held at 65 ° C for about 1 hour until the concentration the NCO groups had fallen to 15%, determined by the wet analysis method described on page 57 in "Organic Functional Group Analysis" by F.E. Critchfield (published 1963 by MacMillan Company), with the difference that tetrahydrofuran is used as the solvent and bromocresol green were used as indicators. The resulting adduct was cooled to room temperature, whereupon 316 g (0.25 equivalent) of HTRLP were added and the mixture to the reaction at 60 ° C with slow stirring leaving an opaque VTRLP product of high viscosity on the order of 1,000,000 mPas at 27 ° C was obtained. The HTRLP used was the addition reaction product of ethylene oxide and a CTRLP and contained about 18% acrylonitrile, about 80% butadiene, and up to about 2% 2-hydroxyethyl acrylate.

Examples 2 to 11

These examples illustrate a two step solution polymerization process, in the case of toluene-2,4-diisocyanate

with 2-hydroxyethyl acrylate to form an adduct implemented and the adduct was then implemented with an HTRLP.

The HEA-TDI adduct was based on that described in Example 1 Way by reacting 43.5 g (0.25 mol) of toluene-2,4-diisocyanate with a mixture of 29.0 g (0.25 mol) of 2-hydroxyethyl acrylate and 0.03 g of phenothiazine, the mixture being added dropwise to the diisocyanate in the course of 15 minutes at 40 ° C. in dry air became. After the mixture had been added, its temperature was increased to 65 ° C. and at 65 ° C. for about 1 hour held. At this point the NCO concentration had fallen to about 15%. The adduct was then brought to room temperature chilled. To a solution of 29.0 g (0.1 equivalent) of the adduct in 75.5 g of styrene was added dropwise with stirring, a solution of 126.5 g (0.1 equivalent) of HTRLP in 80 g of styrene within 2 hours at room temperature given in dry air. After the addition was complete, the reaction continued for a further 8 hours at room temperature continued. The viscosity of this VTRLP was 1070 mPas at 27 ° C. The same HTRLP as in Example 1 was used. The dates and conditions for this experiment and other similar experiments are Compiled below in Table A, in which the amounts given are parts by weight, if not stated otherwise.

Tabel

Two-stage process carried out with a styrene solution 1,600 3 4 5 6th 7th 8th 9 10 (D. 1.5 hr) (0) 11 Attempt no. 2 (10) 87.0 29.0 29.0 29.0 29.0 29.0 29.0 23.2 35 RT 23.2 HEA-TDI adduct 29.0 14.5 14.5 14.5 14.5 14.5 . 14.5 14.5 14.5 4th 8th 14.5 NCO% 14.6 379.5 126.5 167.8 190.0 203.0 175.3 175.0 140.0 0.07 0.09 150.4 HTRLP 126.5 64-110 64-110 90-27 90-33 90-33 90-33 90-33 90-33 1025 7400 90-33 Attempt no. 64-110 75 75 500 500 500 60 60 500 gel gel 500 Phenothiazines ppm 75 50 50 50 50 50 50 50 50 (D (D 50 Styrene,% 50 1.0 1.0 1.0 1.11 1.16 1.07 1.07 1.07 1.11 Total OH / NCO 1.0 L HTRLP TO NCO to
NCO HTRLP HTRLP TO
NCO . NCO too
HTRLP NCO TO
HTRLP HTRLP TO NCO to NCO ZV
NCO HTRLP HTRLP L NCO too
HTRLP Order and
Type of addition HTRLP too
NCO (D. 2.5 hr) (0) (D. 3 hr) (0) (0) (D . 2.5 hr) (0) (D. 2 hr) RT RT RT 35 35 35 RT Temp, ° C RT 18 19 21st 6th 4th 3 8th Time, hours 11 - 0.22 0.09 0.07 0.06 0.09 "vr / ^ a ' r * xt 0.1 1070 2100 3700 1200 1250 Μ 200 5000 Brookfield viscosity
at 27 ° C: mPas 1070 5500 gel gel Gel 1 250 gel J
aged (8th) (1) (3) (3) (10) (D (Days) D: drop by drop (time of addition)
0: all at once
RT: room temperature

As Table A shows, the VTRLP obtained showed acceptably good stability when the HTRLP was added to the adduct was added dropwise as in Examples 2 and 8. However, if the adduct matches the HTRLP was added dropwise or all at once, the obtained VTRLP gelled in a few days. It appears thus that the order of addition of the ingredients is important and if gel formation within a short time should be avoided, the addition of the adduct to the HTRLP should be avoided.

The same HTRLP products as in Example 1 were used in this experiment. Your physical properties are listed in Table B below.

Tabel B. 90-27 90-33 90-37 Product No. 64-110 0.057 0.070 0.073 OH, ÄphH ^X 0.079 0.007 0.001 0.006 COOH, ÄphH * 0.002

Brookfield viscosity at 27 C,

mPas 158,000 158,000 168,000 113,000

H ₂ O Content,% - 0.126 0.095 0.116 ^K ÄphH = equivalents per 100 parts resin.

Examples 12-18

A one-step process for making VTRLP is illustrated by experiments performed using the Materials were carried out with stirring in the following order: HTRLP, solvent, 2-hydroxyalkyl acrylate and a diisocyanate.

Following the procedure outlined for the one-step process, the reaction was carried out as follows: 17.4 g (0.1 mol) of toluene-2,4-diisocyanate became a mixture of 126.5 grams (0.1 equivalent) of HTRLP, 11.6 grams (0.1 equivalent) of 2-hydroxyethyl acrylate, and 12 mg (75 ppm) of phenothiazine placed in 155.5 g of styrene. The mixture was there

initially at room temperature / and the diisocyanate was added dropwise in dry air with stirring. After the addition of the diisocyanate, the temperature of the mixture rose to 32 ° C. in about half an hour. The reaction finished in four hours. The VTRLP obtained had a viscosity of 4750 mPas at 20 ° C. The details and conditions for these experiments are given below in Table C / where the amounts of the materials turn out to be Understand parts by weight unless otherwise specified.

Example no.

Table C. One-step process with styrene solution

13th

14th

16

17th

HTRLP HEA 126. 5 100 7th 300 Linal RT 6th 300 6th 300 300 (1: 4 5) (1:45) 100 > »
¹ >'\, Attempt no. TDI 90-27 90-27 90-27 24 7th 90-27 5 90-27 90-27 RT " RT 90-37 VD>> »>» Styrene 11. 6th 7th 3 21. 1920 3 21. 1 21.6 21.6 23 23 7.4 OH / NCO 17th 4th 11 0 29 07 28. 11 29.7 28.5 1560 1520 9.9 I.
ι ι »>
» Type of addition (hours) 155. 5 119. pir 351 350 351.3 350.1 117.3 » * * >
» Temp, ° C - 1. 1. 1. 1.07 1.11 1.16 I.
Ϊ J
i ι t Time, hours _ _on >
»» ·
* * >
• »> Br viscosity at 27 ° C, Servings RT RT RT 25-35 4th 23 24 12th inPas - 3350 1725 9 30

For the definition of HTRLP, see Table B.

Examples 19-22

These experiments illustrate the manufacture of a VTRLP using a two step solution process in which a mixture of 2-hydroxyethyl acrylate and phenothiazine is added as a stabilizer to form an adduct with 4,4'-methyldiphenyl diisocyanate (MDI). An already described solution of HTRLP in Styrene is added and the reaction is completed as described in the previous examples. The details and conditions of these processes are set forth in Table D, where the amounts of materials are parts by weight, unless otherwise specified.

19th Brook fieId-Vi skos itat 11,000 20th 21st 22nd Table D. 109.8 at 27 ° C, mPas 12,400 29.3 29.3 29.3 11.5 Aged 10 10.7 10.7 10.7 379.5 Days 0.5% 140.2 150.1 150.1 Two-stage process with styrene solution 64-110 NCO treatment Methanol 90-33 90-33 90-33 Attempt no. ι 75 500 500 500 HEA-MDI adduct 47 50 50 50 NCO,% 1/0 1.07 1.11 1.11 HTRLP on e i η m a I drop by drop Attempt no. 22-30 22-35 24-27 22-28 Phenothiazine, ppm 6th 8th 8th 5 Styrene,% 0.11 0.06 0.06 0.128 OH / NCO Addition of MDI 7000 4000 3550 Temperature, ⁰ C 10,400 7200 7800 Time, hours 5 5 3 A _n C ₀ M _0n 100 ppm 100 ppm 300 ppm Ethylene Ethylene Triethanol

glycol glycol amine

4,4'-methylenediphenyl diisocyanate is at room temperature a white or light yellow fused solid and above 38 ° C a clear yellow liquid. For use in the experiments described here it was melted. As the table above shows, this is Hydroxy1 / isocyanate ratio inversely proportional to the Viscosity of the VTRLP formed. For example, by increasing the hydroxy / isocyanate ratio of 1.0 to 1.11 the viscosity of the VTRLP obtained from 11,000 to 4,000 mPas at 27 ° C. The reaction temperature during the first 2-3 hours of the reaction should be kept below about 25 C to keep the viscosity of the product below about 3000 mPas at 27 ° C In a preferred embodiment, should the temperature during the first 2 to 3 hours of the reaction will be about 20 to 22 ° C. The reaction temperature can then be increased to a value in the range from 30 to 40 ° C in order to accelerate the reaction complete.

20 Examples 23 to 29

These experiments illustrate the one-step solution process already described, which is based on the one described in the preceding corresponding examples using 4,4'-methylenediphenyl diisocyanate (MDI) with 2-hydroxyethyl acrylate and HTRLP was performed. The details and conditions for these experiments are given below in Compiled in Table E, where the amounts of materials are parts by weight, unless otherwise specified.

* ■ ». ψ

Tabel

HTRLP One-step process with styrene solution 24 25th 35-42 26th 27 28 29 Attempt no. Product No. 23 300 700 3 300 300 300 300 HEA 300 90-33 90-33 0.05
9000 90-33 90-33 90-37 90-37 MDI 90-33 22nd 8 50.4 27,500 21.6 21.6 22.2 22.2 Phenothiazine>, ppm 22.8 48. 9 95.6 2 41.0 41.0 42.7 42.7 Styrene,% 48.9 500 500 200 ppm
p-toluene
sulfone
acid 500 5Q0 500 500 OII / NCO 500 50 50 50 50 (ToI. '' O 50 50 MDI addition 50 1. .00 1.11 1.11 1.11 1.20 1.20 Temp., ⁰ C 1.00 drop-on
wise once on
once on
once on
once drops
, way Time, hours on
once 21-38 22-33 22-32 22-38 21-22 ^A NCO ^{/ A} CN
'Br. Viscose, at 27 ° C 22-33 2 5 5 7th 8th 'Aged 3 · 12,000 0.07
5000 0.05
3400 0.2
2500 0.56
. 2400 Days , mPas 9000 - 5250 3700 .2300 3700 NCO treatment - 3 3 12th 1 200 ppm
Tri-
ethanol
amine 200 ppm
Tri
ethanol
amine 500 ppm
Tri-
■ ethanol
amine no

• Toi. = Toluene

r-o CO CO

Claims (8)

Claims 1. Process for the production of reactive liquids Polymers with terminal vinyl groups, characterized in that one isocyanate with a hydroxyl compound containing ethylenic double bonds and a terminal hydroxyl group Reacting reactive liquid polymer containing. 2. The method according to claim 1, characterized in that the isocyanate is a diisocyanate and the hydroxyl compound a monohydroxyl compound selected from the hydroxyalkyl esters of unsaturated acids, hydroxyl groups containing alkenes and vinyl aromatic alcohols and a terminal hydroxyl group containing reactive liquid polymer with a bulk viscosity in the range used from 5000 to 2,000,000 mPas. 3. The method according to claim 1 or 2, characterized in that the diisocyanate from aliphatic and aromatic diisocyanates that contain hydroxyalkyl esters of unsaturated acids with 1 to 12 carbon atoms Contain alkyl radical and the unsaturated acids Telephone: (0221) 131041 Telex: 8882307 dopo d Telegram: Dompaten! Cologne _ O - aliphatic and aromatic acids with 2 to 8 carbon atoms are selected, the hydroxyl-containing alkenes contain 1 to 12 carbon atoms, the vinyl aromatic Alcohols the formula _n -0H in which R and X are individually selected ^from hydrogen, halogens and alkyl radicals having 1 to 4 carbon atoms, and η is a number from 0 to 12. 4. In the presence of a solvent carried out method according to claim 3, characterized in that the relative molar proportions of the reactants are about 2 moles of the hydroxyl compound, about 2 moles of the Isocyanate and about 1 mole of the liquid polymer containing terminal hydroxyl groups, the hydroxyalkyl esters contain 2 to 8 carbon atoms in the alkyl radical, of which one or more substituents from the halogens, nitrates, carbonates, substituted or unsubstituted alkyl radicals with 1 to 4 carbon atoms, alkoxy, alkenoxy and substituted and unsubstituted phenoxy groups can, the hydroxyl-containing alkenes are selected from 1-alkenes having 2 to 8 carbon atoms, where the hydroxyl group is on the terminal carbon atom, and the vinyl aromatic alcohols up to Contain 4 radicals X on the aromatic ring, where η is a number from 0 to 4. 5. The method according to claim 4, characterized in that the reaction at a temperature of about 20 to 70 ° C carried out, about 1.05 to 1.3 mol of the hydroxyl compound per mole of the diisocyanate reacted, as a solvent one that is not reactive with the isocyanate groups Solvent used, the hydroxyl compound of substituted and unsubstituted hydroxyalkyl acrylates and methacrylates with 2 to 4 carbon atoms in Alkyl radical which can carry alkoxy and / or alkenoxy radicals as substituents is selected. 6. The method according to claim 4 and 5, characterized in that the alkyl radical in the hydroxyalkyl acrylates and -methacrylate substituents from the group consisting of acryloxy, methacryloxy, crotonoxy, allyloxy, methoxy, ethoxy, Propoxy and butoxy radicals can contain. 7. The method according to claim 1 to 6, characterized in that the reactive liquid polymer with terminal hydroxyl groups from butadiene-acrylonitrile copolymers with terminal hydroxyl groups, butadiene-acrylonitrile-hydroxyethyl acrylate with terminal Hydroxyl groups, butadiene-styrene copolymers with terminal hydroxyl groups, epichlorohydrin polymers with terminal hydroxyl groups, polybutadiene with terminal hydroxyl groups and butadiene-alkyl acrylate copolymers with terminal hydroxyl groups. 8. The method according to claim 1 to 7, characterized in that the hydroxyl compound is added to the isocyanate an adduct and then the reactive liquid polymer containing terminal hydroxyl groups reacts with the adduct in the presence of a solvent and thereby the reactive liquid polymer forms with terminal Viny! groups.