JPH0565531B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a novel polyester/polysiloxane copolymer. (Prior Art) In recent years, resins or resin mixtures containing polysiloxane polymers have attracted attention. As is well known, polysiloxane polymers have excellent physicochemical properties such as heat resistance and cold resistance, so they can be used for primary products such as rubber (silicone rubber), oil, and varnish, as well as for various secondary products using them as raw materials. is put into practical use. Furthermore, in recent years, research has been conducted in a wide variety of fields to develop various functions of polysiloxane polymers while maintaining the above-mentioned physicochemical properties. For example, in the field of engineering plastics, research is being conducted to utilize their low-temperature elasticity to create large tubes and hoses with low-temperature impact resistance, and in the field of medical materials, their biochemical stability is being utilized to create orthopedic materials, blood vessels, etc. Many products have already been put into practical use as prosthetic materials, ointment base materials, etc. Furthermore, its usefulness is attracting attention in the field of gas separation membranes from the standpoint of resource and energy conservation. The gas separations targeted here include the separation and purification of recycled gases such as helium purification, rare gas separation, uranium enrichment, oxygen enrichment, ethanol synthesis, and acetic acid synthesis. It has been put into practical use because of its improved efficiency. Methods for producing resins or resin mixtures containing polysiloxane polymers include the following. (1) A method of directly kneading a polysiloxane polymer with other resins is described, for example, in JP-A-58-93749, Plastics.
It is described in World p.70 March, 1983, etc. (2) Methods for producing block copolymers by chemically combining polysiloxane polymers with other polymers such as polyesters, polyethers, polyurethanes, and polycarbonates include, for example, WL
Roff, Ann.NYAcd.Sic., 146 , 119 (1967),
WJWard, J.Mom.Sci., 1, USP3.781, 378
etc. are listed. (3) A method of graft polymerizing polysiloxane to a suitable backbone polymer is described, for example, in JP-A-57-135007;
Described in Proceedings of the Society of Polymer Science 31 , 461 (1982). (4) A method of synthesizing a polymer by anionic polymerization of a polymerizable group containing polysiloxane as a substituent in the side chain is described, for example, in Japanese Patent Publication No. 52-21021. Among the above-mentioned various manufacturing methods, the manufacturing method suitable for inventing mechanical, electrical, and physical properties depending on the use of the resin is the polysiloxane method described in (2) above from the viewpoint of ease of molecular design. It is thought that this method involves chemically combining a polymer with another polymer to obtain a block copolymer. In addition, so-called polyester resins obtained from dicarboxylic acid components and glycol components have long been known to have excellent mechanical properties, heat resistance, and abrasion resistance, and are used in household and industrial appliances. Many uses are known, such as in electronics, equipment, electronic industry parts, and automobile parts. However, when used in automotive parts, better low temperature flexibility than normal polyester resins is required. For this reason, polyester elastomers using polyether instead of the glycol component of polyester are often used in such applications. (Problems to be Solved by the Invention) However, such polyester and polyether copolymers have the problem of significantly decreasing their physical properties in the low temperature range of 0 to -40°C. Therefore, there have been problems in that oil resistance is poor because of the ester bond, and hydrolysis resistance is insufficient due to the ester bond.The present invention aims to provide a resin that can solve these problems. The purpose of the present invention is to provide a new group of aromatic polyester resins having a polyorganosiloxane component.The polyorganosiloxane component is incorporated into the aliphatic polyester chain to be used as a mold release agent or a leveling agent. A proposal for obtaining polymers useful as agents is disclosed in U.S. Pat. No. 3,935,154 and involves reacting a diol-rich aromatic polyester with a small amount of a polyorganosiloxane component having polyoxyalkylene chains at both ends. The proposal to obtain a polymer with improved adhesion and blocking properties by
Although disclosed in No. 4348510, the polymer of the present invention has not been known at all. (Means for Solving the Problems) As a result of intensive research, the present inventors have found that while maintaining the properties of aromatic polyester, the excellent properties of polyorganosiloxane (heat resistance, water absorption resistance, hydrolysis resistance, The present invention was completed by discovering a new polyester copolymer with chemical resistance, etc.). (Structure of the Invention) Thus, the present invention has the following general formula (): (In the formula, R'' represents a lower alkylene group) and the following general formula (): (In the formula, l is an integer of 2 to 50, m is an integer of 1 to 6, Q is an oxygen atom or one bond, R' is a hydrogen atom, a methyl group or a phenyl group, R is a divalent organic group, ) is a polyester copolymer whose main constituent units are units represented by the formula (), and the copolymerization ratio of the units of the formula () to the units of the formula () is 40 to 99 by weight.
60-1 and a J-value of 10-300 ml/g. In the present invention, the ratio between the units of formula () and the units of formula () is such that the units of formula () are approximately 40 to 99% by weight based on the total weight of both units, in other words, the units of formula () are approximately 40% to 99% by weight. It is said to be 60 to 1% by weight. If the unit of formula () is less than 40% by weight, the inherent properties of polyester will be impaired and the J-value will be extremely low, making it unsuitable. If it exceeds 99% by weight, the polyorganosiloxane-containing units of formula () will become too small, and the original properties of the polyorganosiloxane, such as low temperature flexibility, heat resistance, hydrolysis resistance, and chemical resistance, will deteriorate. Significantly degraded and unsuitable. A particularly preferred ratio is unit():unit() of approx.
50-97% by weight: approximately 50-3% by weight. The J-value of the polyester copolymer of this invention is 10
~300ml/g, preferably 20-250ml/g.
The J-value [ml/g] is an index value for evaluating the solution viscosity of a polymer and indirectly defines the molecular weight of the copolymer of the present invention, and its measurement method is as follows. [Deutsche Industrie Norm (DIN)
16779Teil2] Accurately weigh 0.25 g of the sample into a 50 ml volumetric flask, and use a 1/1 mixed solvent of phenol/O-dichlorobenzene to dissolve the sample at room temperature or by heating to bring the total volume to 50 ml. Next, using an Ubbelohde viscometer at 25°C, measure the falling time of only the solvent and the falling time of the solution containing the sample. J-
The value can be calculated using the following formula. J-value = (falling time of solution/falling time of solvent only) -
1/sample viscosity (=0.5 g/ml) [ml/g] Note that ηrel (relative viscosity) = fall time of solvent/fall time of only solvent. This J-value can usually be adjusted as appropriate by adjusting the amount of esterification catalyst, esterification time, addition of a monofunctional third component described below, and the like. As the phthalic acid residue constituting the units of formulas () and () of the present invention, terephthalic acid residues or isophthalic acid residues are suitable, and these may be used in combination. Usually, it is preferable to have a total composition of 100 to 20% terephthalic acid residues and 0 to 80% isophthalic acid residues. R'' in the formula () of the present invention includes a lower alkylene group, especially an optionally branched alkylene group having 2 to 4 carbon atoms, especially an ethylene glycol residue or a 1,4-butylene group. Glycol residues are preferred. R in the formula () of the present invention is a divalent organic group, and an alkylene group which may have a branch, 1 to
About 4 moles of polyoxyethylene residues, divalent alicyclic groups, or divalent aromatic groups are suitable. In addition,
As the divalent alicyclic group, a divalent group containing at least an alicyclic hydrocarbon group can be used, and as the divalent aromatic group, a divalent group containing at least an allyl group can be used. The above alkylene group may be a straight chain or branched alkylene group.
_C2-20 alkylene groups are preferred, and branched alkylene groups include, for example

【formula】

【formula】

Examples include [Formula]. Specific examples of divalent alicyclic groups include:

【formula】

[Formula] (Optionally substituted with lower alkyl group)
etc. In addition, specific examples of divalent aromatic groups include: (which may be optionally substituted with a lower alkyl group), and the like. Note that the divalent aromatic group may optionally have an ether bond, a sulfonyl bond, a sulfide bond, or a carbonate bond, and specific examples thereof include: etc. Note that the hydrogen atoms in each of the above groups may be optionally substituted with a halogen atom. On the other hand, R' in formula () means a hydrogen atom, a methyl group or a phenyl group. These groups are usually the same group, but may be different depending on the case. Such a polyester copolymer of the present invention usually has the following formula (): phthalic acid or its C ₁ to C ₄ alkyl ester represented by the following formula (): HO−R″−OH ... () (in the formula, R″ has the same meaning as above); The formula below (): (In the formula, each symbol has the same meaning as above.) It is obtained by polymerizing a polyorganosiloxane component represented by the following by an SL reaction. As such a polymerization method, a method (one-stage method) in which each component represented by the above formulas (), (), and () is polymerized by subjecting them to esterification reaction conditions at once is common. More specifically, for example, terephthalic acid and/or
Or an aromatic dicarboxylic acid component such as isophthalic acid (formula ()) and ethylene glycol or 1,4
- A diol component such as butanediol (formula ()) and a terminal diol-type polyorganosiloxane represented by the above formula () are mixed, and this is mixed at a temperature of 170 to 280°C in the presence of an esterification catalyst. The reaction is carried out by heating under a normal pressure inert gas flow, then the polycondensation is carried out by heating at 200 to 280°C under a reduced pressure of 30 mmHg or less, preferably 10 to 15 mmHg, and further under high vacuum (for example, 1 mmHg or less, preferably 0.1 mmHg).
(below), the polyester copolymer of the present invention having a high molecular weight can be obtained by carrying out heating polycondensation at 220 to 280°C. In this case, for the components of the above formula (), the formula ()
It is practically preferable to set the total number of moles of the components of formula () and formula () to be approximately equal, and furthermore, in order to correspond to the copolymerization ratio of units (): The weight ratio of about 40 to 99: about 60 to 1
It is preferable that Further, as the esterification catalyst for the ester bond, tin-based catalysts, titanium-based catalysts, lead-based catalysts, etc. can be used. For example, dialkyltin oxides such as dibutyltin oxide and dioctyltin oxide; dibutyltin urarylate, dibutyltin dialkyltin alkylates such as bis(2-ethylhexanoate); tetraalkyl titanates such as tetramethyl titanate, tetrabutyl titanate, tetraisopropyl titanate; titanium oxalates such as potassium titanium oxalate; such as lead acetate Examples include lead compounds. Among these, titanium-based catalysts such as tetraalkyl titanates and titanium oxalate salts give the best results and are preferred. The polyester copolymer obtained in this way is a mainly linear copolymer obtained by reacting the formula () with the formula () in substantially equimolar amounts. units () and ()
It consists of a copolymer in which are bonded in a random manner. However, in some cases, a prepolymer (one end is a carboxyl group or its lower alkyl ester and the other end is a hydroxyl group) corresponding to the unit () and/or the component of the unit () is prepared in advance, and then these are esterified. It can also be obtained by subjecting it to chemical reaction conditions and polymerizing it (two-step method). The polyester copolymer obtained by this method consists of a copolymer in which units ( ) and/or units ( ) are bonded together in a block shape. As the compound of formula () which is the raw material, compounds available under the names of so-called terminal diol type polyorganosiloxane, double-terminated hydroxy polyorganosiloxane, silicone diol, etc., or modified products thereof can be used. A particularly preferable example is the following formula: (In the formula, p is an integer of 2, 4 or 10; q is an integer). The polyester copolymer of the present invention has excellent low-temperature flexibility in the low temperature range of 0 to -40°C due to the low Tg (glass transition temperature), which is a characteristic of polyorganosiloxane. Due to the excellent water resistance of polyorganosiloxane, which acts as a polymer, it has extremely excellent hydrolysis resistance even though it is a polymer with ester bonds. The copolymer of the present invention may be a copolymer having at least the above-mentioned units () and () as main constituent units, and other tertiary units may be added to the polymer chain as long as the above-mentioned properties are not impaired. may have. Examples of the third component that can constitute the third unit include various dicarboxylic acids, diols, and oxycarboxylic acids that can be linearly copolymerized through ester bonds. Of course, when copolymerizing these third components, it is preferable to adjust the total dicarboxylic acid component and diol component to be substantially equimolar. Further, it is usually appropriate to adjust the amount of the structural unit of the third component (third unit) to be less than 50 mol% of the total structural units. These third components include aromatic dicarboxylic acids other than phthalic acid; oxalic acid, malonic acid, succinic acid,
Aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and dodecanedioic acid; Alicyclic dicarboxylic acids such as hexahydroterephthalic acid, decalindicarboxylic acid, and tetralindicarboxylic acid; Oxyacids such as glycolic acid and p-oxybenzoic acid; Alicyclic diols such as methanol and tricyclodecane dimethylol; bisphenol A, bisphenol S, bishydroxyethoxybisphenol A,
Aromatic diols such as tetrabromobisphenol A are exemplified. As other third components, carboxylic acids other than dicarboxylic acids and alcohols other than diols can be used. Examples include trimellitic acid, trimesic acid, pyromellitic acid, tricarballylic acid, trimethylolpropane, glycerin,
Examples include polyfunctional compounds such as pentaerythritol, and monofunctional compounds such as benzoic acid, naphthonic acid, stearyl alcohol, valmitic acid, and derivatives thereof. In particular, this polyfunctional compound
The polyester of the present invention can be used to the extent that it can be considered substantially linear, and monofunctional compounds are suitable for use in adjusting the molecular weight of the polymer. In addition, the polyester copolymer of the present invention further contains a heat stabilizer such as phosphorus, an antioxidant such as hindered phenol, and an ultraviolet absorber such as benzotriazole, hydroxybenzophenone, and cyanoacrylate, just like ordinary polyester. , titanium oxide,
There is no problem even if pigments such as carbon black and tetradull blue, dyes, nucleating agents such as talc, crystal accelerators such as higher fatty acid salts, mold release agents, etc. are added. EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 29.15g (0.15mol) dimethyl terephthalate
And the following formula: 1.35 g of both-terminated butanoloxypolydimethylsiloxane with a number average molecular weight (Mw) of 1247
(5% by weight based on the entire diol component) and 1,
25.65 g of 4-butanediol were placed in a one-cylinder flask, and 0.9 g of isopropyl titanate (Ti(OC ₃ H ₇ ) ₄ ) solution in isopropyl alcohol (10%) was added as a catalyst. This mixture was stirred at 180° C. for 3 hours using a metal bath while introducing nitrogen gas. For another 30 minutes, the temperature of the metal bath was raised to 70°C while the pressure was reduced to 15mmHg using a water jet pump. After further heating and stirring at 250°C under reduced pressure for 1 hour, the pressure was reduced to 0.05 mmHg or less using a high vacuum pump, and stirring was continued at 250°C for another 1 hour. The product was removed under nitrogen to give a white, highly viscous polymer. The J-value of this polymer was determined using phenol/O-dichlorobenzene (1/1) as the solvent.
When measured in °C, it was 99. In addition, from the infrared absorption spectrum, a slight absorption was observed at 800 and 1000 to 1100 cm ^-1 , which is the characteristic absorption of polydimethylsiloxane, and from 1HNMR, the absorption of methyl groups bonded to the silyl groups of polydimethylsiloxane was observed at 0.1 ppm. was recognized. From the above, it was confirmed that this polymer is a copolymer of polyester and polydimethylsiloxane. This copolymer was subjected to DSC (Mettler
TA-2000 type and PerkinElmer type 2C), Tg is 54℃ and Tm (melting point) is 223℃.
It turned out to be. Examples 2 to 6 Various polyester copolymers were produced in the same manner as in Example 1. Table 1 shows the physical properties of this raw material and the obtained copolymer.

[Table] (Effects of the invention) As mentioned above, the polyester copolymer of the present invention exhibits particularly excellent physical properties in terms of low-temperature flexibility and hydrolysis resistance, and also has various properties as a polyester. Therefore, it is suitable for use as a resin for manufacturing sealing materials such as hoses, tubes, seals, and packing, or belts such as caterpillars and belts.

Claims (1)

[Claims] 1. The following general formula () (In the formula, R'' represents a linear lower alkylene group) and the following general formula (): (In the formula, l is an integer of 2 to 50, m is an integer of 1 to 6, Q is an oxygen atom or one bond, R' is a methyl group, and R is a linear or branched lower alkylene group) It is a polyester copolymer whose main constituent units are the units of formula () and the copolymerization ratio of the units of formula () to the units of formula () in a weight ratio of 40 to 99:
60-1 and a J-value of 10-300 ml/g. 2. The polyester copolymer according to claim 1, wherein the phthalic acid residues in the main constituent units of the polyester copolymer consist of 100 to 20% terephthalic acid residues and 0 to 80% isophthalic acid residues. Polymer.