DE1720177B2 - Process for the production of thermoset diene polymers - Google Patents

Description

The German patent 16 45 503 relates to a process for the production of heat-cured diene polymers by reacting a polyfunctionally substituted one produced by anionic polymerization Polydiene prepolymer with a polyfunctional organic chain extender, which is able to react with the functional groups of the diene prepolymer, at room temperature or moderately elevated temperature and hardening of the chain-extended product with the aid of heat and a hardener. This process is characterized in that one is polyfunctionally substituted Diene prepolymer one whose polymer structure has predominantly 1,2-configuration is used and the peroxide initiator, which is used as hardener and provides free radicals, even before the chain-lengthening reaction to the diene prepolymer is added, with the chain extension reaction below the activation temperature of the peroxide initiator works and the hardening after the chain extension reaction by increasing the temperature above the activation temperature of the peroxide initiator

Hiirrh leads.

177 ₂

In the implementation of the polyfunctionally substituted polydiene prepolymer with the polyfunctional one Organic chain lengthening agent initially creates an elastomeric material, which is dependent Has vinyl groups. By increasing the temperature above the activation temperature of the free radical-generating peroxide initiator, the pendant vinyl groups are caused to react, so that hard plastics are created, which are made up of molecular chains of cross-linked, condensed cyclohexane rings exist, which are linked with hydrocarbon chains. It is believed that these resins in structural terms mainly from blocks of crosslinked linear chains of condensed substituted or unsubstituted cyclohexane rings and blocks of saturated or unsaturated hydrocarbon groups exist. The blocks of fused substituted or unsubstituted cyclohexane groups are with each other with the blocks of saturated or unsaturated hydrocarbon groups linked by groups that are derived from the reactive groups of the polydiene prepolymer and of the organic chain extender.

The method of the earlier right 16 45 503 is characterized in that it is initially an elastomeric Intermediate product that is easily shaped and shaped can be handled and which is then converted into a hard resin by further heating can be.

Similar polymers are known from US-PS 31 09 871, but are known to be polyfunctional in their production Substituted diene prepolymer is used, the polymer structure of which is predominantly Has 1,4 configuration. The one with a peroxide initiator however, cured products have an elastic rubber-like shape.

According to the invention it has now been established. that by incorporating certain long-chain polyfunctional hydrocarbon prepolymers in the reaction mixture of the process of the older Right 1645 503 set the hardness of the product obtained after curing with the peroxide initiator can.

The invention therefore relates to a process for the production of heat-cured diene polymers by reacting a polyfunctionally substituted one prepared by anionic polymerization Polydiene prepolymer with a polyfunctional organic chain extender, which mil the functional groups of the diene prepolymer is able to react at room temperature or moderately elevated temperature and hardening of the extended chain product with the aid of heat and a hardener where a polyfunctionally substituted diene prepolymer is one whose polymer structure has predominantly 1,2-configuration, used and used as hardener, which produces free radicals Peroxide initiator is added to the diene prepolymer before the chain extension reaction, with mar work in the chain lengthening reaction below the activation temperature of the peroxide initiator and the hardening after the chain extension reaction by increasing the temperature via the Akti The conversion temperature of the peroxide initiator is carried out according to patent 16 45 503, which is characterized by this net is that you rush in the implementation of the diene before polymer with the Celtic lengthening agent

long-chain hydrocarbon prepolymer with a molecular weight between 250 and 3000 from the group 1,4-polybutadiene diol homopolymer, dihydroxy 1,4-polybutadiene / styrene copolymer, dihydroxy-1 ^ -polybutadiene / acrylonitrile copolymer, at, hydrogen-saturated 1,4 - Polybutadiene diol homopolymer, hydrogen-saturated dihydroxy-1,4-polybutadiene / styrene copolymer, hydrogen-saturated dihydroxy-1,4-polybutadiene / acrylonitrile copolymer, hydrogen-saturated 1,2-polybutadiene diol homopolymer or polyisobutylene homopolymer.

The functional groups of the polydiene prepolymer and the hydrocarbon prepolymer are preferably at the ends of the prepolymers. Although difunctional prepolymers which are characterized by a terminal substitution are preferred, other prepolymers with, for example, a terminal and a non-terminal group can also be used. The polydiene prepolymer preferably used is a 1,2-polybutadiene diol with hydroxyl substituents on the end groups of the prepolymer.

The details of making the 1,2-isomeric form the polydiene prepolymer and its subsequent cyclization are already in the older one German patent 16 45 503 indicated. The polydiene prepolymers, which are used to prepare the polymer according to the invention should have at least 80% of the olefinic unsaturation in the form of vinyl groups on alternating carbon atoms of the carbon backbone. The molecular weight should be from about 500 to about 3000.

Saturated or partially unsaturated hydrocarbon diols can be used as hydrocarbon prepolymers be used. It is important that the hydrocarbon prepolymer does not contain any large amounts contains vinyl groups attached to alternating carbon atoms in the basic chain. In this way During the cyclization of the polydiene blocks, considerable amounts of the hydrocarbon blocks do not occur at the same time cyclized. A typical hydrocarbon prepolymer is 1,4-polybutadiene diol with hydroxyl substituents at the end groups of the prepolymer.

The polydiene prepolymer and the hydrocarbon prepolymer are with the polyfunctional organic chain extender in the presence of the peroxide initiator reacted, advantageously being carried out after mixing a degassing will. In the case of dihydroxy prepolymers and a diisocyanate chain extender the chain extension reaction at room temperature or moderately elevated temperatures, being a rubber-like intermediate product is obtained, which is characterized in that in it the free radicals delivering peroxide initiator is molecularly distributed. A heating of the rubbery intermediate product Temperatures of about 70 to 140 ° C result in cyclization of the vinyl groups of the polydiene block with the formation of condensed substituted or unsubstituted cyclohexane rings and with crosslinking of the neighboring chains.

The organic chain extender is usually a difunctional compound, but which is can also contain more than two functional groups. Will be the preferred polyfunctional organic Chain extenders with a dihydroxypolydiene and with dihydroxy hydrocarbon prepolymers, for example 1,2-polybutadiene diol and 1,4-polybutadiene diol. used then as a chain extender an organic diisocyanate preferred, resulting in urethane groups.

When the urethane groupings are formed, no condensation products, such as, for example, are formed Water or ammonia. The absence of a volatile condensation product makes the reaction particularly suitable for the production of adhesive bonds, laminates and compact resin masses. In addition, the urethane copolymer mixture is pourable, and after the reaction, the a moderately low temperature takes place, a long shelf-life, non-sticky rubber-like material is obtained. The urethane rubber obtained in the diisocyanate reaction is molecular with a Free radical-producing peroxide initiator permeated, which is responsible for the cyclization and crosslinking reaction is required for obtaining the hard thermosetting resin.

The chemical structure of the reaction of 1,2-polybutadiene diol and 1,4-polybutadiene diol with 2,4-toluene diisocyanate in the presence of free radicals The polymers obtained from the supplying peroxide catalysts are as follows:

HO-CH ₂ -CH ₂ -C-CH ₂ -HC

Il

CH ₂
Dihydroxy-1,2-polybutadiene

H
C-CH,

H-C

Il

CH ₂

-C-CH ₇ -C-CHj-CHj-OH

OCN

H-C

Il

" CH ₂

HC
CH,

Toluene diisocyanate

+ HO-CH ₂ -CH

Dihydroxy-1,4-poly butadiene

Chain extension with the formation of polyurethane elastomer intermediates

--0-CH ₂ -CH ₂ -C-CH ₂

R-CH ₂

-C-CH ₂ -

H-C -_

Il '

^ CH,

-C-CH ₂ -C-CH ₂ -CH ₂ -CH ₂ -OCN

H-C. H-C.

. I! \ Il "

; - CH, "* CH,

H-N

O = C

N-C-O-CH, -CH, -fCH, -CH = CH-CH ₂ ^ -CH ₂ -CH ₂

R: R ?. R Cyclization of the vinyl groups and crosslinking

-Q-CH ₂ -CH ₂ -

R-CH

-CH ₂ -CH ₂ -CH ₂ -OCN

CH,

to the networking point

Η — Ν
I.
OC

NCO-CH ₂ -CH ₂ HCH ₂ -CH = CH-CH ₂ ^ cH ₂ -CH ₂

In the above reaction scheme, η represents a number of such a size that the molecular weight of the cyclized part of the molecule is about 500 to 3000, while m is such Of value is that the molecular weight of the long chain hydrocarbon portion of the molecule is approximately 300 to 3000.

In the manufacture of these resins, for example, a polydiene diol prepolymer is thoroughly treated with a long-chain hydrocarbon diol, an organic diisocyanate and a free radical donor Mix the peroxide initiator until a homogeneous consistency is achieved. The polydiene diol and the hydrocarbon diol can be used in any desired ratio, but the diisocyanate in an approximately stoichiometric amount with respect to the polydin / hydrocarbon diol mixture should be used. The peroxide is generally used in an amount between 0.5 and 10 percent by weight, preferably between 2 to 6 percent by weight, based on the weight of the Prepolymers and the diisocyanate chain extension agent used.

A chain extension reaction takes place at room temperature or moderately elevated temperatures, whereby an elastomeric intermediate product is formed, which is characterized in that the peroxide initiator producing free radicals is molecularly distributed in it is. While the polymer is in this elastomeric state, it can be handled in a simple manner and processed. After the final item is completed, the rubbery one becomes Intermediate product heated to 66-204 ° C, followed by cyclization and crosslinking to form a hard and transparent plastic that is resistant to impact takes place. Its hardness judges depends on the amount of long-chain hydrocarbon diol used.

The resins obtained according to the invention can be use in a wide variety of fields of application. They can be used as laminates, fillers, hard Foams, films and coatings can be used, to name just a few application examples. As a result their unique intermediate elastomeric state provides considerable relief processing.

The following examples illustrate the invention.

example 1

52 parts of a 1,2-polybutadiene diol with a 2000 average molecular weight, 63 parts of a 1,4-polybutadiene diol with an average Molecular weight of 3000 and 2.3 parts of di-tert-butyl peroxide are placed in a glass vessel given and mixed thoroughly. 9V2 parts Toluene diisocyanate are then added to the kettle, whereupon the solution is stirred until it becomes homogeneous. The solution is in a vacuum chamber with an applied vacuum of approximately Degassed 1mm Hg for approximately 15 minutes. After the degassing period is over, the material will poured into a mold and subsequently hardened under the following hardening conditions:

1. 12 days at 90 ° C in air,

2. 7 days at 115 ° C in air.

The hardened resin is clear, transparent and hard and has a yellow color. A typical casting has the following physical properties:

Hardness 4 barcol

Specific heat 0.348 CaW ⁰ Qg

Decomposition temperature 465 ° C

(in nitrogen) Example 2

104 parts of a 1,2-polybutadiene diol with an average molecular weight of 2000, 62.4 parts of a 1,4-polybutadiene diol with an average molecular weight of 3000 and 3.3 parts of di-tert-butyl peroxide are placed in a glass vessel and mixed thoroughly with one another. Then 14 parts of toluene diisocyanate are added to the vessel, whereupon the solution is stirred for so long until it becomes homogeneous. The solution is in a vacuum chamber at an applied vacuum of degassed approximately 1 mm Hg for approximately 15 minutes. After the degassing period has ended, the The material is poured into a mold and subsequently hardened under the following hardening conditions:

1. 18 days at 90 ° C in air,

2. 8 days at 115 ° C in air.

The hardened resin is clear, translucent, and hard, and is yellow in color.

A typical casting has the following physical properties:

Hardness 15 barcol

Specific heat 0.380 calf C / g

Decomposition temperature 467 ° C

(in nitrogen)
Example 3

53 parts of a 1,2-polybutadiene diol with an average molecular weight of 2000, 124.7 parts of a 1,4-polybutadiene diol with a average molecular weight of 3000 and 3.6 parts of di-tert-butyl peroxide are placed in a gas vessel given and mixed thoroughly. Then 14 parts of toluene diisocyanate are added to the vessel, whereupon the solution is stirred until it becomes homogeneous. The solution is in a vacuum chamber degassed with an applied vacuum of approximately 1 mm Hg for approximately 15 minutes. To At the end of the degassing period, the material is poured into a mold and successively under it hardened under the following hardening conditions:

1. 18 days at 90 ° C in air,

2. 8 days at U 5 ° C in air.

The hardened resin is clear, translucent, and hard, and is yellow in color.

A typical casting has the following physical properties:

Hardness 0 barcol

Specific heat 0.405 cal / ° C / g

Decomposition temperature 467 ° C

(in nitrogen) Example 4

52 parts of a 1,2-polybutadiene diol with an average molecular weight of 2000, 105.9 parts of a 1,4-polybutadiene diol with an average molecular weight of 2000 and 3.2 parts of di-tert-butyl peroxide are placed in a glass vessel and mixed thoroughly. Then will 14 parts of toluene diisocyanate are added to the vessel, whereupon the solution is stirred until it is homogeneous will. The solution is placed in a vacuum chamber with an applied vacuum of approximately 1 mm Hg degassed for approximately 15 minutes. After the degassing period has ended, the material is in poured a mold and successively hardened under the following hardening conditions:

1. 18 days at 90 ° C in air.

2. 8 days at 115 ° C in air.

The hardened resin is clear, translucent, and hard, and is yellow in color.

A typical casting has the following physical properties:

Hardness 0 barcol

Specific heat 0.320 calf C / g

Decomposition temperature 467 ° C

(in nitrogen) Example 5

52 parts of a 1,2-polybutadiene diol with an average molecular weight of 2000, 62.4 parts of a 1,4-polybutadiene diol with an average molecular weight of 2000 and 2.3 parts of di-tert-butyl peroxide are placed in a glass vessel and mixed thoroughly. Then will 14 parts of bitolylene diisocyanate are added to the vessel, whereupon the solution is stirred until it is homogeneous will. The solution is placed in a vacuum chamber with an applied vacuum of approximately 1 mm Hg Degassed for about 15 minutes. After the degassing period has ended, the material is turned into a Poured in the form and subsequently under the following Hardening conditions hardened:

1. 11 days at 90 ⁰ C in air,

2. 9 days at 115 ° C in air.

509548/398

The hardened resin is clear, semi-translucent and solid and yellow in color.

A typical casting has the following physical properties:

Hardness 0 barcol

B c: i s ρ i e 1 6

52 parts of a 1,2-polybutadiene diol with a 2000 average molecular weight, 53 parts of a 1,2-polybutadiene diol with a average molecular weight of 2000 and 2.1 parts of di-tert-butyl peroxide are placed in a glass vessel given and mixed thoroughly. Then 14 parts of bitolylene diisocyanate are added to the kettle, whereupon the solution is stirred until it becomes homogeneous. The solution is in a vacuum chamber degassed with an applied vacuum of approximately 1 mm Hg for approximately 15 minutes. After completion During the degassing period, the material is poured into a mold and successively under the hardened under the following hardening conditions:

1. 11 days at 90 ⁰ C in air,

2. 9 days at 115 ° C in air.

The hardened Han. is clear, semi-translucent and solid and yellow in color.

A typical casting has the following physical properties:

Hardness 0 barcol

Example 7

62 parts of a 1,2-polybutadiene diol with an average molecular weight of 2000. 52 parts of a 1,4-polybutadiene diol / acrylonitrile copolymer with an average molecular weight of 2500 and 2.3 parts of di-tert-butyl peroxide are placed in a glass jar and mixed thoroughly. Then 14 parts of bitolylene diisocyanate are added added to the kettle, whereupon the solution is stirred until it becomes homogeneous. The solution will be in a vacuum chamber with an applied vacuum of about 1 mm Hg for about 15 minutes long degassed. After the degassing period is over, the material is poured into a mold and sequentially cured under the curing conditions specified below:

1. 11 days at 9O ⁰ C in air,

2. 9 days at 115 ° C in air.

The hardened resin is clear, semi-translucent, and solid, and is yellow in color.

A typical casting has the following physical properties:

Hardness 0 barcol

Claims (1)

Claim: 17th 2, Process for the production of heat-cured diene polymers by reacting a through polyfunctionally substituted polydiene prepolymer produced with anionic polymerization a polyfunctional organic chain extender, which with the functional Groups of the diene prepolymer to react ι ο able to at room temperature or moderately elevated temperature and hardening of the chain-extended Product with the help of heat and a hardener, which is used as a polyfunctionally substituted diene prepolymer one whose polymer structure has predominantly 1,2-configuration is used and the peroxide initiator, which is used as hardener and provides free radicals, even before the chain-lengthening reaction is added to the diene prepolymer, the chain extension reaction being below the activation temperature of the peroxide initiator works and the hardening after the chain extension reaction by increasing the temperature above the activation temperature of the peroxide initiator Patent 1645 503, characterized in that the reaction of the diene prepolymer with the chain extender, a long-chain hydrocarbon prepolymer with a molecular weight between 250 and 3000 from the group of 1,4-polybutadiene diol homopolymer. Dihydroxy - 1,4 - polybutadiene / styrene copolymer, Dihydroxy-1,4-polybutadiene / acrylonitrile copolymer, hydrogen-saturated 1,4-polybutadiene diol homopolymer, hydrogen-saturated dihydroxy-1,4-polybutadiene / styrene - Copolymer, hydrogen-saturated dihydroxy -1,4 - polybutadiene / acrylonitrile copolymer, hydrogen-saturated 1,2-polybutadiene diol homopolymer or polyisobutylene diol homopolymer used.