JPH03122117A - Resin for vibration-deading material - Google Patents

Abstract

PURPOSE:To obtain the title resin having excellent vibration damping properties, heat resistance, weather resistance, molding and processing properties, consisting of specific two kinds of aromatic polyesters and a block copolymer of the polyester and a polyorganosiloxane. CONSTITUTION:The objective resin consisting of (A) an aromatic polyester comprising an aromatic dicarboxylic acid (e.g. terephthalic acid), a dihydric phenol (e.g. hydroquinone), and one or more diol selected from a lower aliphatic diol (e.g. ethylene glycol) and an alicyclic diol (e.g. cyclohexanediol), (B) an aromatic polyester comprising an aromatic hydroxycarboxylic acid (e.g. m- hydroxybenzoic acid) and (C) a block copolymer comprising an aromatic polyester selected from copolymers composed of the components A and B and a polyorganosiloxane.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel resin for vibration isolating materials, and more particularly to a resin for vibration isolating materials that has an excellent vibration damping effect over a wide temperature range.

[Problems to be solved by conventional technology and invention]

Various anti-vibration materials have been developed using polymeric materials, and their applications are wide-ranging, including home appliances, electronic computers, and machinery and equipment in material factories for transportation equipment such as automobiles and aircraft. .

Most of these anti-vibration materials using polymeric materials utilize the viscoelastic properties of polymers, particularly the phenomenon of increase in loss coefficient near the glass transition of the material. Therefore, the temperature range in which the anti-vibration effect can be exhibited is limited to a narrow temperature range near the glass transition point of the material used. Furthermore, in view of the viscoelastic properties of polymeric materials, there is a correspondence between temperature and vibration frequency, so the frequency is also limited to a narrow range. As a result, its uses are extremely limited.

Since polyorganosiloxane exhibits stable physical properties over a wide temperature range, a vibration-proof rubber composition made by blending butyl rubber with polyorganosiloxane (
JP-A-54-41957, JP-A-56-7644
4) has been proposed, but it does not provide a vibration isolating material that can be used in a wide temperature and frequency range. Furthermore, all of these rubber compositions require a vulcanization process, and once they have been vulcanized, they become thermoplastic and cannot be recycled. The invention can maintain excellent vibration-proofing effects in a wide range of temperatures and frequencies that are not found in conventional vibration-proof rubber.
Another object of the present invention is to provide a resin for vibration isolating materials that can be easily molded using normal molding methods.

As mentioned above, polyorganocloxane has a small loss tangent and poor vibration damping effect, but it generally has a glass transition temperature in an extremely low temperature range, so it has stable viscoelastic properties over a wide temperature range around room temperature. It has the characteristic of holding .

The present inventors focused on the stable properties of this polyorganosiloxane, and as a result of intensive study on a method of increasing the loss tangent at room temperature without changing its glass transition temperature, the inventors found that polyorganosiloxane and aromatic polyester It was discovered that the object could be achieved by block copolymerization, and the present invention was achieved.

That is, the gist of the present invention is (a) an aromatic polyester comprising an aromatic dicarboxylic acid and one or more diols selected from dihydric phenols, lower aliphatic diols, and alicyclic diols; (b) aromatic hydroxycarboxylic acid; Aromatic polyester consisting of an acid and a copolymer consisting of (c) (a) and (1) .

The polyorganocloxane used in the present invention has the following formula C
I) has a repeating unit represented by (wherein R, and R2 each independently represent a methyl group or a phenyl group, and n represents an integer of 5 or more).

Aromatic dicarbonate used in the present invention, the following formula [■]
: HO-0-R3-0-OH (■) [In the formula, R3 represents a substituted or unsubstituted] unicine group, the following formula: -C-. ) or a naphthylene group. ] Here, examples of the substituent of the phenylene group include chlorine, bromine, methyl group, etc., and the substituted phenylene group can be substituted with 1 to 4 substituents.

Such aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, diphenyl-p,p'-dicarboxylic acid, diphenyl-'p,p'-dicarboxylic acid, diphenylmethane-p,m'-dicarboxylic acid, diphenylmethane-p, , p'-s) carboxylic acid, benzophenone-4,
Examples include 4'-dicarboxylic acid and naphthalene dicarboxylic acid, and these can be used alone or in combination of two or more. Further, a small amount of aliphatic dicarboxylic acids such as adipic acid and sepacic acid may also be mixed and used.

Next, examples of the dihydric phenol include hydroquinone, resorcinol, dihydroxynaphthalene, biphenol (biphenyldiol), 1,8-dihydroxyanthraquinone, and an alkylene group having 5 or less carbon atoms. ), such as 2,2-bis(4-hydroxyphenyl)furopane (bisphenol A), 4.4'-
! /Hydroxydiphenylhydroxy V diphenylketone, 4.4'-dihydroxydiphenylmethane, 1.1-
Bis(4-hydroxyphenyl)-ethane, 1,1-his(4-hydroxyphenyl)-butane, 1,1-bis(4-hydroxyphenyl)-2,2,2-trichloro-ethane, etc. These may be used alone or in combination of two or more t'i.

Examples of lower aliphatic diols include alkylene diols having 2 to 6 carbon atoms, such as ethylene glycol, propylene gellicol, 1,4-butanediol, t5-bentanediol, and 1°6-hexanediol. Examples of the alicyclic diol include cyclohexanediol and cyclohexane dimetatool.

These may be used alone or in combination of two or more.

The aromatic hydroxycarboxylic acid used in the present invention has the following formula: % formula % [wherein, R is a phenylene group, and the following formula: (wherein, X is a direct bond or an alkylene group having 5 or less carbon atoms] ) or a naphthylene group.

] It is indicated by.

Examples of such aromatic hydroxycarboxylic acids include m-hydroxybenzoic acid, p-hydroxybenzoic acid, 1-hydroxy-6-naphthoic acid, 2-(4'-hydroxyphenyl)-2-(a'- (carboxylphenyl)-propane, 4-hydroxyphenyl-4-carpoki V-phenyl ether, etc., and these may be used alone or in combination of two or more.

Preferred polyester segments include an aromatic polyester consisting of terephthalic acid and 1,4-butanediol, a mixture of terephthalic acid and isophthalic acid, and Otsu 2-
Aromatic polyester consisting of bis(4-hydroxyphenyl)propane, copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, p- and dolo*Vbenzoic acid, 2,6-naphthalene dicarboxylic acid and 2.6
- Copolymers of naphthalene diol or copolymers of p-hydroxybenzoic acid, 2,6-naphthalene dicarboxylic acid, resorcinol and isophthalic acid.

Further, the aromatic polyester used for the polyester segment may be a polyester exhibiting liquid crystallinity.

The aromatic polyester-polyorganosiloxane block copolymer of the present invention can be produced using known melt condensation polymerization, solution condensation polymerization, interfacial condensation polymerization, etc., which are suitable depending on the components constituting the aromatic polyester and the functional groups of the polyorganosiloxane. It can be manufactured by a method.

For example, for a block copolymer of terminal alkylamine type polydimethyl V-loxanth aromatic polyester,
AC3, PO], 7m prop (1q 85) and 3
0 th National sAMPIC8qmos
ium March 19-21.1985 k according to the method described. In addition, a block copolymer of terminal dimethylamine type polydimethylsiloxane and aromatic polyester is manufactured by Kng, Kng, Ohem, P.
rod, Ree, Deve-1op,, Vol, 1
2.44.1975 and TRANSAC Engineering 1ON80F
THE Boo EngineeringEiTY 0PREICOLOGY
21: 2.273-290 and mpplied Po
lymer 8qmposium 422.143-1
56 (1973) and 30th National S
AMPEi sympo-sium March 19
-21.1985. In addition, a method in which a terminal diol type polyorganosiloxane, an aromatic dicarboxylic acid civalide, and a dihydric phenol are used as a dehydrochlorination agent for a tertiary amine such as pyridine in a halogenated organic solvent such as chloroform at 50°C or lower, and an aromatic A block copolymer can also be produced by melt condensation polymerization of a diol-type polyorganosiloxane at both terminals represented by a compound or an aromatic polyester constituting a group polyester in the presence of a transesterification catalyst, and which method can be used. I can't help it.

The aromatic polyester-polyorganosiloxane block copolymer of the present invention has a polyorganosiloxane content of 25 to 75% by weight, more preferably 30 to 60% by weight, from the viewpoint of vibration damping effect and heat resistance.

To the thus obtained block copolymer of the present invention, heat stabilizers, antioxidants, ultraviolet absorbers, mold release agents, flame retardants, flame retardant aids, etc., and/or pigments, dyes, etc. may be added. can.

Further, the block copolymer of the present invention can be pelletized by a normal extrusion process and then molded into a desired shape by extrusion molding, injection molding, pressure molding, or the like.

[For production]

The resin for vibration isolating materials made of the aromatic polyester-polyorganosiloxane block copolymer of the present invention has the advantages of aromatic polyester in addition to the advantages of polyorganosiloxane and has improved the disadvantages, so it is better than conventional vibration isolating materials. It can be a useful resin for vibration-proof materials because it shows superior vibration-proofing properties, heat resistance, cold resistance, and weather resistance compared to ordinary resins, and can be easily molded into buttons.

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, it goes without saying that the present invention is not limited to these.

〔Example〕

Example 1 Dimethyl terephthalate 040kl; +, 1,4-butanediol (L21kg) and both-terminated hydroxyphenethylpolydimethylsiloxane (number average molecular weight 830) represented by the following formula (p is an integer of 5 or more) α75 with a stirrer Butyl titanate (
A 1 weight solution of Ti(OOaH4)i') in butanol was added. The mixture was heated under stirring at a temperature of 150-250° C. for 4 hours in a nitrogen gas atmosphere. After that, the pressure was gradually reduced to 250°C, and the temperature was increased for 2 hours.
It was set to 5 mHg. After further stirring for 3 hours at 250° C. and α5■HE, the reaction was terminated and a high viscosity polymer was recovered.

Example 2 Example except that 49 kg of dimethyl terephthalate α, 9 for 1,4-butanediol α 30, and 060 kl of both-terminated hydroxyphenethyl polydimethylsiloxane (number average molecular weight 830) represented by the formula [M] in Example 1 were used. Polymerization was carried out in the same manner as in 1 to obtain a high viscosity polymer.

Example 3 Dimethyl terephthalate α56k11.1.4-butanediol (135 kg and formula (A) in Example 1)
Polymerization was carried out in the same manner as in Example 1, except that 50 kg of both-terminated hydroxyphenethyl polydimethylsiloxane (number average molecular weight 8'50) α shown in was used to obtain a high viscosity polymer.

Example 4 Dimethyl terephthalate α69kg, 1,4-butanediol α45kg and Example 1 except that both ends represented by the formula (A”!) and droxyphenethylpolydimethylsiloxane (number average molecular weight 830) 130ml were used. Polymerization was carried out in the same manner as in Example 1 to obtain a high viscosity polymer.

Example 5 Dimethyltere7tale) (L72ki9.1,4-butanediol (L51 kg and in Example 1 the formula (A
) Polymerization was carried out in the same manner as in Example 1, except that 25 kg of both-terminated hydroxyphenethylpolydimethylsiloxane (number average molecule Ji-830) α was used to obtain a high viscosity polymer.

Example 6 Polydimethylsiloxane with diol at both ends (
number average molecular weight 1100) rl, 50 kli, prephthalic acid chloride and isophthalic acid chloride, respectively (L20
'Kg into a reactor with a stirrer, 2.5k of chloroform
g was added to make a homogeneous solution.

Next, bisphenol Aa, 52 kit chloroform 1
．． 5U and pyridine (L31 and 9) were dissolved in a mixed solvent to make a homogeneous solution, which was added to the above solution that had been cooled to 0°C.

After stirring for 7 to 8 hours, the reaction solution was taken out, washed with dilute hydrochloric acid and water, and poured into methanol to recover the polymer.

Example 7 Both terminal diol type polydimethylsiloxane (number average molecular weight 1010000) shown by formula CB in Example 6
150, terephthalic acid chloride, and isophthalic acid chloride (115) were each placed in a reaction vessel equipped with a stirrer, and chloroform & Okg were added to make a uniform solution.

Next, 32 kg of bisphenol A [1 L] was dissolved in a mixed solvent of 32 kg of chloroform a, 0 kg of pyridine (L23) to make a homogeneous solution, and the solution was added to the above solution that had been cooled to 0°C.

After stirring for 7 to 8 hours, the reaction solution was taken out, washed with dilute hydrochloric acid and water, and poured into methanol to recover the polymer.

Example 8 Terephthalic acid chloride and isophthalic acid chloride were each mixed with CL15, bisphenol AQ,! 50 kg of chloroform and 25 kg of pyridine were charged into a reaction vessel equipped with a stirrer and a condenser tube, and the mixture was refluxed for 4 to 5 hours.

The reaction solution was taken out, washed several times with dilute hydrochloric acid and water, and then poured into methanol to obtain a double-terminated bisphenol A aromatic polyester (number average molecular weight 6,000) 11.42k.
I got g.

Next, 142 kg of this double-terminated bisphenol A aromatic polyester, 138 kg of double-terminated dimethylaminoborodimethylchloroxane (number average molecular weight 5.400) represented by the following formula: (a represents an integer of 10 or more), and chlorobenzene 5. 5 kg was charged into a reaction vessel equipped with a stirrer and a cooling tube, and after refluxing for 12 hours, it was reprecipitated with methanol.
A polymer was obtained.

Example 9 Both-terminated hydroxyphenethylpolydimethylsiloxane (number average molecular weight 830
) to a, 1) cg, p-acetoxybenzoic acid (L(15
4klI, Toki on 1-7-! /-6-f phthoic acid n
Os2, 9 and terephthalic acid Q,006 were placed in a wide container equipped with a stirrer, and 50 ppm of tetrabutyl titanate was added as a catalyst.

After heating this material at 230°C for 3 hours under a nitrogen atmosphere, the temperature was further raised to 300°C over 30 minutes, and the temperature was increased for 15 seconds.
The pressure was reduced to wHH. After heating at 300° C. and t5 mHg for 1 hour, the pressure was reduced to α5WHg, and after further heating for 1 hour, the product was taken out to obtain a high viscosity polymer.

Example 10 Both terminal diol-type boridimethylroxane (number average molecular weight 1,500) 2 shown by the formula CB used in Example 6
．． 5# and dimethyl terephthalate) 1.94 to 9,
Cyclohexane dimetatool 2.68 to 9 was charged into a reaction vessel equipped with a stirrer, and butyl titanate (
150 - of a 1]i't% butanol solution of Ti(OO4Hs)4) was added. This mixture was mixed in a nitrogen gas atmosphere.
It was heated at a temperature of 200C to 310C for 4 hours while stirring.

Thereafter, the pressure was gradually reduced to 115 mHg at 310°C over 2 hours. Furthermore, 310℃, CL5mw
After stirring for 2 hours under Hg2 conditions, the reaction was completed and a highly viscous polymer was obtained.

Example 11 The polymers obtained in Examples 1 to 10 described above were
After extruding into pellets, injection molding was performed to obtain specimens for paper measurement. Using this, the anti-vibration effect was evaluated by measuring the impact resilience, which is related to the loss tangent. This impact resilience) refers to the ratio of recovery energy to deformation energy when a test piece is deformed by applying an impact, and the smaller the value, the larger the loss tangent, and the lower the vibration isolation effect. Indicates good condition. The impact resilience was measured in accordance with J.K. 8-6301. In addition, as a weather resistance test, the specimen was stored in SO'C for 30 days, and then the impact resilience was measured.

The results are shown in Table 1.

Comparative Example 1 100 parts by weight of methylphenylvinyl polysiloxane raw rubber, 50 parts by weight of reinforcing agent ST II, and 1 part by weight of vulcanizing agent were mixed together, and 20 parts by weight of polyisobutylene having a viscosity average molecular haze of about 10,000 was blended therewith. After kneading with a roll for 15 minutes, the mixture was vulcanized by heating and pressurizing at 170° C. for 10 minutes to prepare a test piece. Using this test piece, the vibration damping effect and weather resistance were measured in the same manner as in the examples. The results are shown in Table 1.

〔Effect of the invention〕

The aromatic polyester-polyorganosiloxane block copolymer of the present invention has excellent vibration damping properties, heat resistance, and weather resistance, and is also easy to mold, so it can be used under harsher conditions than before. It can be used as a resin for vibration isolating materials that can be used in a wider range of applications.

Claims (1)

[Claims] 1) (a) an aromatic polyester comprising an aromatic dicarboxylic acid and one or more diols selected from dihydric phenols, lower aliphatic diols, and alicyclic diols; (b) aromatic hydroxyl; A vibration-damping resin comprising an aromatic polyester comprising a carboxylic acid, and a block copolymer of an aromatic polyester selected from a copolymer comprising (c) (a) and (b) and a polyorganosiloxane.