DE2535562A1 - Vulcanisable copolymers of unsaturated polyester and rubber components - from unsaturated lactones and cyclic olefins or conjugated dienes - Google Patents

Abstract

Copolymer comprises units (I) =(CH-R-COO-R1-CH)= and (II) -(CH-R2-CH)-. R and R1 consist of -(CH2)m-gps. where m = 1-13. Either or both of R and R1 can be alkyl and/or aryl substd. and can opt. contain additional olefinic double bonds. R and R1 together should contain 3-14C atoms. R2 comprises a methylene chain -CnH2n-, where n = 2-10; a methylene chain -Cn+2H2n+2- with one olefinic double bond, where n = 2-8 or a methylene chain -Cn+4. H2n+4- with two olefinic double bonds, where n = 2-6 with the restriction that >=1 double bond is unconjugated. Copolymers are useful as elastomers, rubbers, foams glass reinforced polyester compsns. and thermosetting resins. In an example, 0.92 mmols each of 16-hydroxy-hexadecenoic-(6)-lactone and cyclooctene were copolymerised for 3h at 90 degrees C in the presence of 0.037 mmol. WCl6 and 0.185 mmol. (CH3)4Sn to give 0.207g copolymer.

Description

Unsaturated polyester-rubber copolymers and processes for their Production The invention relates to new, high molecular weight, unsaturated, linear polyester-rubber copolymers whose nonomer units consist essentially of unsaturated lactones and cycloolefins or from unsaturated lactones and unsaturated polymers from cycloolefins or conjugated dienes, and a process for their preparation.

In the Dr patent application are homopolymers of unsaturated Lactones with ring sizes of 7-17 have been proposed, which make the structure more unsaturated Polyesters of the general formula iCH - R - COO - R'-CH. in the R and R 'unsubstituted or alkyl- and / or aryl-substituted methylene groups with or represent without further olefinic double bonds.

The invention is based on the surprising finding that it is possible to use the unsaturated lactones with cycloolefins or with unsaturated To copolymerize polymers from cycloolefins or conjugated dienes.

The copolymers of the invention are 1) true copolymers since the Cycloolefins or unsaturated ones used as comonomers in the copolymerization Lactones are present in the form of their monomer units in each polymer chain and 2) Copolymers with a random distribution of the monomer units.

The structure of true copolymers is proven, among other things, by that the gel chromatographic analysis in no case indicates the presence of bimodal or asymmetric molecular weight distributions, i.e. for the presence of 2 homopolymers of different molecular weight.

When the copolymer is broken down at the double bond in the presence of a Low molecular weight olefin with olefin metathesis catalysts turned out to be practical quantitatively detectable polymer fragments by gas chromatography, which with the help of mass spectrometric Identification of the products the presence of the monomer units used in to prove a real copolymer structure.

The unsaturated lactones used according to the invention for the copolymerization have a ring size of 7-17 atoms and have the general formula in the R and R 'methylene groups (CH2) m. with m from 1-13, which at the same time or independently of one another are alkyl- and / or aryl-substituted and can optionally contain further olefinic double bonds, where R and together comprise 5-14 atoms. Examples of unsaturated lactones are 6-hydroxy-hexen (5) acid lactone, 12-hydroxy octadecen (9) acid lactone (ricinoleic acid lactone), 16-hydroxy hexadecen (6) acid lactone ( Ambrettolide), 15-hydroxy-octadecadien- (9,12) -acid-lactone and the like.

The general inventive concept of course also includes, instead of the lactones mentioned above, unsaturated lactones of the structure to use. R, R1 and R'1t are methylene groups - (CH2) -m, where m for R, Rr and R "'is at least equal to 1, in the case of structure (I) m of Rtt' can also be zero.

The methylene groups can also be alkyl- and / or aryl-substituted.

The cycloolefins have the general formula in the R "methylene groups -CnH2n- with n of 2 - 10 or a methylene chain with an olefinic double bond Cn + 2H -with n of 2 - 8 or a methylene chain with two olefinic double bonds Cn + 4H2n + 4 together with the condition that at least one olefinic double bond is not conjugated. The methylene groups can also be independently alkyl- and / or aryl-substituted and halogen and ester-substituted. All cycloolefins in which the double bonds are configured cis, trans or cis / trans can be used according to the invention Examples of cycloolefins are cyclopentene, cycloheptene, cyclooctene, cyclododecene, cyclooctadiene- (1,5), cyclododecatriene- (1,5,9), instead of cyclooiefins it is also possible to use unsaturated polymers made from cycloolefins or conjugated dienes from cycloolefins are polypentenylene, polyheptenylene, polyoctenylene, polydodecenylene.

Examples of the polydienes are, on the one hand, the 1,4-polydiolefins like 1,4 PDlybutadiene and 1,4 polyisoprene and on the other hand the 1,2-polydiolefins such as 1,2 polybutadiene and 1,2-polyisoprene.

The copolymers according to the invention have units of the general type Formulas iCH - R - COO - R '- CH + and = [= CH - R "- CH =] = where R and R1 are methylene groups (CH2) m with m from 1-13, which at the same time or independently of one another are alkyl and / or be aryl-substituted and optionally contain further olefinic double bonds can, where R and R 'together have 3-14 carbon atoms and Rtt methylene groups -CnH2n- with n of 2 - 10, a methylene chain. with an olefinic double bond -c n + 2H2n + 2 -with n of 2 - 8 or a methylene chain with two olefinic double bonds Cn + 4R2n + 4 with n of 2 - 6 means together with the condition that at least one olefinic double bond is not conjugated. The methylene groups can also independently of one another alkyl- and / or aryl-substituted and halogen- and ester-group-substituted be.

In the case of the copolymers, especially unsaturated lactones with 1,2-P; wlydiolefins, branched copolymers are formed from 1,2-polydiolefins with polyester-containing side chains, where p denotes the degree of polymerization of the grafted polyester side chain, and crosslinked copolymers of polyester-linked 1,2-polydiolefins, where q denotes the degree of polymerization of the polyester-containing network length.

All of the olefinic compounds mentioned can be used in all molar ratios can be used in combinations of two or more.

The monomer units in the copolymers according to the invention have im essentially the structure of unsaturated polymers. as can be seen from 1H-NMR measurements the constitution of the copolymers results.

According to the invention, the copolymerization is carried out in the presence of a metathesis catalyst system carried out, which has been obtained by mixing the following ingredients: a) a Tungsten or molybdenum salt, b) an organometallic compound or a Hydride of a metal from group IL - IV, in particular Al, Sn, Mg and Zn, and optionally c) an electron donor compound.

The connection mentioned under c) is not absolutely necessary, however, enables the reaction rate to be increased.

The tungsten salts that can be used particularly advantageously include for example WC16 and WOCl4.

Examples of the organometallic compound or the metal hydride are RnAlCl3 n, (where R is an alkyl group and n = 1-5), (R) 4Sn (where R is a Alkyl group and n = 1 - 8), LiAlH4, NaBH4 alkyl Mg Hal. Alkyl Zn Hal and the like. Particularly good results are obtained when tetraalkyltin compounds or C 2H5AlCl2 can be used.

Examples of the electron donor compound are carboxylic acids, peroxides, Alcohols, phenols, triphenylphosphine and the like.

The molar ratio between transition metal and organometallic compound is expediently in the range from 1: 0.5 to 1. 100. When using (CH5) 4Sn the molar ratios are advantageously in the range between 1: 1 and 1:20 The molar ratio between the transition metal salt and the monomers is expediently in the range from 1: 5 to 1: 10,000. Particularly good results are obtained when this Ratio is in the range between 1:10 and 1: 200.

The order in which the various components of the catalyst mixture are added can be varied.

However, it is best to first use the comonomers then optionally the electron donor compound, then the transition metal salt and finally to add the organometallic compound.

The inventive copolymerization of the unsaturated lactones with Cycloolefins or with unsaturated polymers can in the presence of an inert diluent be performed. Suitable diluents are, for example, aliphatic, cycloaliphatic and aromatic hydrocarbons such as e.g.

Hexane, cyclohexane and chlorobenzene. Particularly good results will be however, achieved when the copolymerization is carried out with as little or no diluent as possible is carried out.

The copolymerization according to the invention is generally carried out at temperatures carried out between - 50 and + 120 ° C, preferably at 0 - 100 ° C. The invention Ccpolymers are in aromatic and chlorinated hydrocarbons such as benzene, Chlorobenzene and CCl4 as well as soluble in ethers such as tetrahydrofuran and in alcohols like methanol and ethanol largely insoluble.

The molecular weights of the copolymers are over 10,000, in some Cases over 100,000, as demonstrated by gel chromatographic determination.

The structural proof of the copolymers can also, ie mentioned, be done by analyzing the degradation products of the copolymers after the metathesis reaction - with a low molecular weight olefin. This is explained below for a typical example. If the metathesis reaction of a copolymer of ambrettolide and cyclooctene is carried out with a sufficiently high excess of octene (4), mainly the following degradation products with predominantly one monomer unit can be detected.

The copolymers of the invention are white solids with fibrous or rubbery appearance. For example, in the field of elastomers, Rubbers, foams, glass fiber reinforced polyesters and thermosetting resins can be used.

The copolymers according to the invention are based on systems Sulfur and accelerators as well as vulcanizable with radical formers such as peroxides or networkable. They can generally be further copolymerized with vinyl monomers.

The copolymers according to the invention can be used during or after the copolymerization Usual additives such as antioxidants, plasticizers, fillers. Colorants, stabilizers, Compounding agents or the like can be added.

The invention is explained in more detail below with the aid of exemplary embodiments explained.

Example 1 In a reaction vessel equipped with a stirrer, nitrogen inlet and outlet pipe as well as a filler neck closed with a septum a dry nitrogen atmosphere is established.

Then 0.92 mmol (0.2) 2 g) ambrettolide and 0.92 mmol (0.101 g) Cyclooctene (each dried and with a purity> 99%) was introduced. To Addition of 0.037 mmol of WC16 in 1 ml of chlorobenzene changes the reaction by 0.185 mmol (CH) 4Sn started. The copolymerization takes place after a reaction time of 5 hours at 90.degree canceled by the addition of methanol. The copolymer precipitated in methanol is cleaned by dissolving several times in chlorobenzene and precipitating with methanol, the methanol containing 0.1% phenyl-§ g -naphthylamine.

0.207 g of copolymer are obtained; the molar ratio of the comonomers Ambrettolide to cyclooctene in the copolymer is 61:39; the copolymer will be at Room temperature and dried under reduced pressure.

The polymer is a white, elastic solid with no sticky properties. The copolymer composition is determined by 1H-NMR spectrometry from the Ratio of the olefinic protons to the ether protons (-COO-CH2-) of the polyester.

The molecular weight is determined by gel chromatography using tetrahydrofuran determined as the eluent and is fi 90,000. The result is a uniform Peak, which speaks for the presence of a true copolymer.

The metathesis reaction of the copolymer with octene (4) gives by gas chromatography separable degradation products which, according to mass spectrometric identification, the used Comonomer units can be assigned. The mass spectrum gives the molecular peaks of the main degradation components M + = 364 and M + = 222, which corresponds to the expected structure of the breakdown products CH3- (CH2) 2-CH = CH- (CH2) 5-COO- (CH2) 8-CH = CH- (CH2) 2-CH3 and CH3- (CH2) 2-CH-CH- (CH2) 6-CE - (CH2) 2-CH) matches.

The copolymer is in aromatic solvents such as benzene and chlorobenzene as well as soluble in chlorinated hydrocarbons such as CCl4 and in alcohols such as methanol and ketones such as acetone are largely insoluble.

Example 2 The procedure is as in Example 1 with the difference that the following reactants are used: 0.92 mmol (0.232 g) ambrettolide, 0.92 mmol (0.063 g) cyclopentene, 0.0) 7 mmol WC16 and 0.185 mmol (CH3) 4Sn.

The reaction temperature is 90 ° C. The isolated as in Example 1, purified and dried copolymer is a white, elastic solid.

0.199 g of copolymer are obtained; the molar copolymer composition is determined by 1H-> 9iR measurement and results for ambrettolide: cyclopentene = 80:20. The molecular weight, determined by gel chromatography, is Mn = 65,000. The mass spectrometric identification of the degradation products of the copolymer according to Metathesis reaction with octene (4) results in an analogous manner for the molecular peaks of Main breakdown components M + = 364 (ambrettolide) and M + = 180 (cyclopentene), what a Corresponds to degradation up to one monomer unit.

Example 5 The procedure is as in Example 1 with the difference that the following reactants are used: 1.22 mmol (0.309 g) ambrettolide, 0.61 mmol (0.066 g) cyclooctadiene- (1.5), 0.037 mmol WCl6 and 0.185 mmol (CH3) 4Sn.

The reaction temperature is 90 C. The isolated as in Example 1, purified and dried copolymer is a white, elastic solid.

0.510 g of copolymer are obtained; the molar copolymer composition is determined by ¹H-NMn measurement and results from ambrettolide: Cyclooctadiene- (1.5) = 2: 1. The molecular weight, determined by gel chromatography, is Mn = 70,000.

The mass spectrometric identification of the degradation products of the copolymer after metathesis reaction with octene (4) results in an analogous manner for the molecular peaks of the main degradation components M = 564 (ambrettolide) and M + = 166 (cyclooctadiene- (1.5)).

M + = 166 corresponds to a breakdown product CH3- (CH2) 2-CH = CH- (CH2) 2-CH = CH- (CH2) 2-CH3 of cyclooctadiene (1.5), since its monomer unit is converted into two by a metathesis reaction further identical sub-units are to be dismantled.

Example 4 The procedure is as in Example 1 with the difference that that the following reactants are used: 0.92 mmol (0.252 g) ambrettolide, 0.92 mmol (0.099 g) cyclooctadiene- (1.5), 0.057 mmol WC16 and 0.185 mmol (CH3) 4Sn.

The reaction temperature is 90 00. The isolated as in Example 1, cleaned and dried Copolymer is a white, elastic Solid. 0.242 g of copolymer are obtained; the molar copolymer composition is determined by 1H-MiR measurement and results from ambrettolide: Cyclooctadiene- (1.5) = 50:50. The molecular weight, determined by teaching chromatography, is Mn = 75,000. The mass spectrometric identification of the degradation products of the copolymer according to Metathesis reaction with octene (4) results in an analogous manner for the molecular peaks of Main breakdown components M + = 364 (ambrettolide) and M + = 166 (cyclooctadiene- (1.5).

Example 5 The procedure is as in Example 1 with the difference that the following reactants are used: 0.92 mmol (0.252 g) ambrettolide, 0.92 mmo (.06s g) cyclopentene, 0.037 mmol WC16 and 0.185 mmol (CH ») 4Sn.

The reaction temperature is 25 ° C. The isolated as in Example 1, purified and dried copolymer is a white elastic solid.

0.22) g of copolymer are obtained; the molar copolymer composition becomes 3 determined by 1H-NMR measurement and results for ambrettolide: cyclopentene = 65 : 37. The molecular weight determined by teaching chromatography is Mn = 105,000. The mass spectrometric identification of the degradation products of the copolymer according to Metathesis reaction with octene (4) results in an analogous manner for the molecular peaks of Main breakdown components Mi = 564 (ambrettolide) and M = 180 (cyclopentene).

Example 6 The procedure is as in Example 1 with the difference that the following reactants used become: 0.92 mmol (0.232 g) ambrettolide, 0.92 mmol based on monomer units (0.050 g) cis 1,4-polybutadiene (Mn = 7000), 0.057 mmol WCl6 and 0.185 mmol (CH3) 4Sn.

The reaction temperature is 90 ° C. The isolated as in Example 1, purified and dried copolymer is a clear, viscous material. It will 0.180 g copolymer obtained; the molar copolymer composition is determined by 1H-NMR measurement determined and results in ambrettolide: polybutadiene = 50:50.

The molecular weight determined by gel chromatography is Mn = 24 000. The mass spectrometric identification of the degradation products of the copolymer after metathesis reaction with octene (4) results in an analogous manner for the molecular peaks of the main degradation components M + = 564 (ambrettolide) and M + = 166 (1,4-polybutades).

Claims (11)

Claims 1.) Unsaturated linear copolymers with units of the general Formula + CH - R - COO - R '- CH} and = [= CH - R "- CH =] = where R and R' are methylene groups - (CH2) m- with m of 1 - 13 represent, which at the same time or independently of one another are alkyl- and / or aryl-substituted and optionally further olefinic double bonds may contain, where R and R 'together have 3-14 carbon atoms, and R11 methylene groups -CnH2n- with n of 2 - 10, a methylene chain with an olefinic double bond Cn + 2H2n + 2 with n of 2 - 8 or an ethylene chain with two olefinic double bonds Cn + 4H2n + 4 with, n from 2 - 6 means with the proviso that at least one olefinic Double bond is not conjugated. 2.) Unsaturated copolymers with units of the general formula where R and R 'have the meaning of claim 1 and p is the degree of polymerization of the grafted side chain of the 1,2-polydiclefin. 3.) Process for the preparation of unsaturated copolymers according to claim 1 or 2, characterized in that one unsaturated lactones with a ring size of 7-17 atoms of the formula with R and R as in claim 1 with olefinically unsaturated compounds, the unsaturated compounds being a) cycloolefins of the formula with Rtt as in claim 1, b) unsaturated polyalkenylenes of the formula + CH - Rtt - CH + with R "as in claim 1 or c) are 1,2-polydiolefins at -50 to + 120 ° C in the presence of a catalyst system copolymerized, which has been prepared by mixing a) a tungsten or molybdenum salt, b) an organometallic compound or a hydride of metals of groups II-IV of the periodic table and optionally c) an electron donor compound. 4.) The method according to claim 3, characterized in that the metals of groups II - IV Al, Sn,; Ng or Zn can be used. 5.) Method according to claim 3 or 4, characterized in that a tungsten halide as the tungsten salt and an aluminum compound as the organometallic compound of the general formula RnAlCl) n in which n represents the integers 1-3, or a tetraalkyltin compound (alkyl) 4Sn is used, the alkyl group of which is 1 - Has 8 carbon atoms. 6.) The method according to claim 5, characterized in that the tungsten halide WC16 is used. 7.) Method according to one of claims 3 - 6, characterized in that that the molar ratio of tungsten or metalloid salt and the organometallic compound is selected in the range from -1: 0.5 to 1:20. 8.) Method according to one of claims 3 - 7, characterized in that that the molar ratio between the tungsten or nolybdenum salt and the copolymerization components (based on monomer units) between 1: 5 and 1: 10,000 is chosen. 9.) The method according to claim 8, characterized in that the molar ratio between tungsten or molybdenum salt and the copolymerization components between 1:10 and 1: 200 is selected. 10.) Method according to one of claims 3 - 9, characterized in that that the copolymerization temperature is 0-100 ° G. 11.) Vulcanized products according to one of claims 3 - 10.