JPS63227627A - Production of polycarbonate based elastomer - Google Patents

Abstract

PURPOSE:To obtain the titled elastomer capable of readily adjusting molecular weight of hard segment and soft segment in one stage, by reacting a polycarbonate oligomer containing chloroformate group with polyether glycol. CONSTITUTION:An aromatic dioxy compound (preferably bisphenol A) is reacted with phosgene to provide a polycarbonate oligomer containing chloroformate group having 2-15 polymerization degree, which is then reacted with a polyether glycol expressed by the formula (m is integer of 2-10; n is integer of 5-100) in a polymerization ratio of 25:75-80:20 to afford the aimed elastomer. The above-mentioned reaction is preferably carried out using tert. amine such as triethyl amine as a catalyst in a solvent such as THF at room temperature - 70 deg.C for 10-120min.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application 1 The present invention relates to a method for producing a polycarbonate thermoplastic elastomer.

[Prior Art 1] Thermoplastic elastomers of A-B-A type block copolymers, which are polymeric materials that exhibit rubber-like properties at room temperature but can be plasticized and molded at high temperatures, have been known. Such thermoplastic elastomers can be rapidly processed using molding machines used for thermoplastic resins and do not require a vulcanization process. ■Elastic bodies with a wide range of physical properties, from soft vulcanized rubber to those close to plastic, can be obtained by changing the chemical structure. (2) The obtained elastic body is thermoplastic because it is not crosslinked, and has the advantage that scraps can be reused.

By the way, one type of such thermoplastic elastomers is polycarbonate-based thermoplastic elastomers, and methods for producing this polycarbonate-based thermoplastic elastomer are disclosed in JP-A-49-133494 and JP-A-51-6.
Methods such as JP-A No. 1597 and JP-A-60-60130 are known, but the technique of JP-A-49-133494 synthesizes the elastomer in two steps.
This method requires a step, and in Japanese Patent Application Laid-Open No. 60-60130, there are drawbacks such as the need to perform the time-consuming adjustment in 1) and 11.

[Problem to be Solved by the Invention 1] The present invention provides a simplified method for producing a polycarbonate elastomer in which the molecular weight of hard segments and soft segments can be easily controlled depending on the application, and the reaction is carried out in one step. The purpose is to

[Means for Solving the Problem 1] The present inventors believe that by using a polycarbonate oligomer, the molecular weight of the hard segment (polycarbonate part) and soft segment (polyether glycol part) can be reduced by one-step homogeneous reaction (polycondensation). The present invention was developed by focusing on the fact that the control can be easily performed.

That is, (Δ) a chloroformate group-containing polycarbonate oligomer with a degree of polymerization of 2 to 15 obtained from an aromatic dioxy compound and phosgene and (B) formula 8 (m is an integer of 2 to 10) The present invention provides a method for producing a polycarbonate elastomer, which is characterized by reacting polyether glycol (an integer from 5 to 100) at a weight ratio of 25:5 to 80:20.

The polycarbonate oligomer used in the present invention is produced by, for example, stirring a mixture of an aromatic dioxy compound such as bis-2-(4-hydroxyphenyl)-propane dissolved in an aqueous solution of caustic soda and an organic solvent such as methylene chloride, and blowing hephosgene into the mixture. , p119 to p12, the introduction of phosgene is stopped and the aqueous layer and organic layer are separated by standing to obtain a solvent solution.

At this time, by appropriately controlling the reaction conditions, the molecular weight of the oligomer and the ratio of hydroxyl groups to chloroformate groups in the molecule can be adjusted as desired.

The polycarbonate oligomer used in the method of this invention has a degree of polymerization of 2 to 15, preferably 3 to 10.
Those having a terminal chloroformate group content of 65% or more can also be used. If the degree of polymerization of the polycarbonate oligomer is less than 2, the crosslinked structure of the finally obtained polycarbonate elastomer will be insufficient and its mechanical strength will decrease. Furthermore, if the degree of polymerization is greater than 15, the rubber elasticity of the polycarbonate elastomer will decrease.

If the content of terminal chloroformate groups in the polycarbonate oligomer is less than 65%, the polycarbonate elastomer production reaction may not proceed sufficiently.

Further, examples of aromatic dioxy compounds used in the production of the polycarbonate oligomer of the present invention include, for example, bis-2-(
4-hydroxyphenyl)-propane, bis-(4-hydroxyphenyl)-methane, bis-2-(4-hydroxy-3,5-dimethylphenyl)-propane, bis-
1-(4-hydroxyphenyl)-butane, bis-3-
(4-hydroxyphenyl)-pentane, bis-1=(
Bis-(4-hydroxyphenyl)-alkane Q, 2.2- such as 4-hydroxyphenyl)-cyclohexane
(3,5,3',5'-tetrachloro-4,4'-dihydroxyphenyl)-propane, 2,2-(3,5,3
',5'-tetrabromo-4,4'-dihydroxydiphenyl)-propane, 2,2-(3,3'-dichloro-
4,4-dihydroxydiphenyl)-propane, 2.2
-(3,5-dichloro4,4'-dihydroxydiphenyl)-propane, 2,2-(3,3'-dichloro-5,
5'-dimethyl-4,4'-dihydroxydiphenyl)
-propane, 2.2-(3,3'-dibromo4.4
'-dihydroxyphenyl)-propane, 3,5.3'
, halogen-containing bispheres such as 5'-tetrabromo-4,4'-dihydroxydiphenylsulfone,
Or 4,4'-dihydroxydiphenylsulfone,
Bisphenols such as 4.4'-dihydroxydiphenyl, 4.4'-dihydroxydiphenyl sulfoxide, and 4.4'-dihydroxydiphenyl ether, and hydroquinone are used, but bisphenol 8 is most preferably used.

The polyether glycol used in the present invention is represented by the formula 8 (Il+ is an integer of 2 to 10, and n is an integer of 5 to 100), and includes, for example, polyethylene ether glycol, polypropylene Ether glycol, polytetramethylene ether glycol, polypentamethylene ether glycol, etc. can be used.

These polyether glycols can be produced by ring-opening polymerization of the corresponding cyclic ethers or polycondensation of the corresponding glycols.

Reaction conditions: temperature room temperature to 70°C, reaction time 10 to 120
It can be carried out under normal pressure or increased pressure.

The degree of polymerization n in the polyether glycol of the present invention is 5
If n is less than 1, it loses its properties as an elastomer, and n is 1.
If it exceeds 00, it becomes difficult to form a block polymer.

The polycarbonate elastomer of the present invention has a weight ratio of polycarbonate oligomer and polyether glycol of 2.
5 is dissolved in a solvent at a ratio of 5 to 80:20, and the solvent in which the catalyst is dissolved is added dropwise to condense it to produce it.

As the catalyst in this case, tertiary amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine are preferably used.

Any solvent can be used here as long as it dissolves both the polycarbonate oligomer and polyether glycol, such as tetrachloroethane, trichloroethane, dichloroethane, trichlorethylene, dichloroethylene, and chloroform. , chlorinated hydrocarbons such as methylene chloride, chlorobenzene, and dichlorobenzene, and cyclic oxy compounds such as dioxane, tetrahydrofuran, and crown ether.

“Example 1 The present invention will be explained in more detail with reference to Examples.

Raw material production example Synthesis of polycarbonate oligomer 40 (60 kg of bisphenol A is dissolved in a 5% caustic soda aqueous solution of V to prepare a caustic soda aqueous solution of bisphenol A. Next, the caustic soda aqueous solution of bisphenol and methylene chloride kept at room temperature are each dissolved at 138 N /hour, 691/hour was introduced into a tubular reactor with an inner diameter of 1011II and a tube length of 10x through an orifice plate, and 10.7 kg of phosgene was cocurrently blown into it at a flow rate of 7 hours, and the reaction continued for 3 hours. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to maintain the discharge temperature of the reaction liquid at 25°C.
and the pl+ of the discharged liquid should be 10 to 11. The resulting reaction solution was allowed to stand still to separate and remove the aqueous phase, and then methylene chloride was removed to obtain a white powdery polycarbonate oligomer.

The degree of polymerization of the oligomer obtained here was 3 to 1.

Example 1 60 g of polycarbonate oligomer produced in Production Example
and polytetramethylene ether glycol (DuPont)
Product name Terratan 1.000:H manufactured by Tsuyapan Limited
n=1003) 49.6y was dissolved in methylene chloride to a concentration of 250.

=8- Next, a solution of 58.5 g of pyridine dissolved in 70 IN of methylene chloride was added dropwise over 30 minutes while cooling with water.

After the addition, the mixture was stirred at room temperature for 60 minutes. After reaction 2N hydrochloric acid 30
0t! The sample was washed twice with water, and then with water until the pH reached 7. Thereafter, methylene chloride was removed to obtain a powdered polymer. The intrinsic viscosity and glass transition temperature of the powdered polymer were measured.

Furthermore, the powdered polymer was molded and the dynamic elastic modulus, breaking strength, and tensile impact strength at 20°C were measured. Further, the hard segment content of the polycarbonate portion was measured by NMR.

Example 2 In Example 1, 70 g of the polycarbonate oligomer used, and polytetramethylene ether glycol of DuPont Tsuyapan Limited product (Teratane 2900) were used.
:Mn=2896) 79.6g and pyridine at 32.
The same procedure was carried out except that the amount was changed to 6 g. The results are shown in the table.

Example 3 The same procedure as in Example 2 was carried out except that 95.6 g of polytetramethylene ether glycol, 409 g of polycarbonate oligomer, and 39.2 g of pyridine were used. The results are shown in the table.

Example 4 In Example 1, 30.1 g of polytetramethylene ether glycol, 76.2 g of polycarbonate oligomer, and 35.0 g of pyridine were used in Example 1. The results were shown in the table in the same manner except that h was used.

Reference Examples 1 to 4 Reference Examples 1 to 4 are polyester thermoplastic elastomers whose hard segments are polybutylene terephthalate (manufactured by DuPont Toshi), Hytrel 4057, and Hytrel 5.
The data on hard segment amount, breaking strength, and tensile impact strength of No. 557, No. 6347, and No. 7247 are shown in the table.

[Effects of the Invention] The thermoplastic polycarbonate elastomer of the present invention can be produced by a one-step reaction, and by selecting the molecular weight and type of the hard segment and soft segment, it is possible to create an elastomer with physical properties suitable for the application. Widely used as exterior, automobile interior materials, separation membranes, filtration membranes, and other industrial materials.

Claims (1)

[Scope of Claims] 1 (A) A chloroformate group-containing polycarbonate oligomer with a degree of polymerization of 2 to 15 obtained from an aromatic dioxy compound and phosgene, and (B) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (m is an integer of 2 to 10, and n is an integer of 5 to 100) in a weight ratio of 25:7.
A method for producing a polycarbonate elastomer, which comprises reacting at a ratio of 5 to 80:20.