JPS59161418A - Preparation of thermoplastic resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin showing flexibility even in the absence of a plasticizer, having high strength, improved oil resistance, heat resistance and freeze resistance, by polymerizing a vinyl chloride monomer (mixture) in the presence of a specific amount of a specified thermoplastic polyurethane elastomer in an organic solvent. CONSTITUTION:100pts.wt. vinyl chloride monomer or monomer mixture of the vinyl chloride monomer and a monomer (e.g., ethylene, etc.) copolymerizable with it is polymerized in an organic solvent (preferably tetrahydrofuran, dimethylformamide) in the presence of 2-300pts.wt., preferably 5-150pts.wt. thermoplastic polyurethane elastomer soluble in the organic solvent, having >=20 deg.C softening point. USE:A coating compound, coating agent for fibers, adhesive, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thermoplastic resin by a solution polymerization method.

More specifically, it relates to a method for producing an organic solvent solution of a thermoplastic resin that is flexible even without plasticization, has high strength, and has excellent oil resistance, heat resistance, and cold resistance. Suitable for use as coating agents, adhesives, etc. Conventionally, polyvinyl chloride and vinyl chloride-vinyl acetate copolymers have been used as vinyl chloride-based paints and adhesives, and in order to provide flexibility In addition, a plasticizer such as dioctyl phthalate (DOP) is usually used in combination. However, paints and adhesives mixed with plasticizers such as DOP have problems with surface contamination, poor heat aging resistance, poor oil resistance, and durability due to migration and scattering of the plasticizer.

The present inventors have completed the present invention as a result of intensive studies aimed at providing vinyl chloride paints, fiber coating agents, adhesives, etc. that have improved these drawbacks.

That is, the present invention provides vinyl chloride monomer (hereinafter referred to as MVC) or vinyl chloride phosphor and a monomer copolymerizable therewith and a monomer mixture (hereinafter referred to as MVC monomer) 100
The kotomer or monomer mixture is polymerized in the organic solvent in the presence of 3 to 200 parts by weight of a thermoplastic polyurethane distomer that is soluble in the organic solvent and has a softening point of 20°C or higher. This is a method for producing thermoplastic resins with special mission.

Next, the method for producing a thermoplastic resin of the present invention will be explained in more detail.

The thermoplastic resin is produced by polymerizing MVC or an MVC monomer in a state dissolved in a TPUt organic solvent. Although the nature of this reaction is not clear, T.P.
It is presumed that some kind of chemical bond (ie, a reaction called so-called graft copolymerization) occurs between U and MVC or MVC monomer.

The TPU in the present invention is one that is substantially soluble in an organic solvent under the solution polymerization conditions of the present invention, and has a softening point of 20° C. or higher. When the organic solvent solution of the thermoplastic resin obtained by the present invention is used as a paint or adhesive, the softening point of the TPU used is 30.
The softening point of TPU is preferably 100-100°C, and when used as a fiber coating agent, the softening point of TPU is 100-200°C.
The temperature is preferably about ℃.

The softening point as used in the present invention refers to the softening temperature determined by the temperature increase method using a Shimadzu height flow tester under the following conditions.

Measurement conditions for Shimadzu Kokata 70-Tester Nozzle dimensions: 1 simple diameter x 2+mL Load: 30kg Heating rate: 3L/min The TPU used in the present invention dissolves in MvC or M'VC type mass. In addition, even if it does not dissolve in these, it may dissolve in an organic solvent such as dimethylformamide or tetrahydrofuran. If the softening point is less than 20°C, the resulting polymer will have poor tensile strength, heat resistance, and oil resistance.

In general, TPU refers to an elastomer having a urethane bond in the molecule, and has a linear block comonomer structure of polyurethane as a soft segment and polyurethane as a hard segment. Usually, soft segments are polymers with hydroxyl groups at both ends.
Hard segments are obtained by reacting glycols or diamines with diincyanates.

As the polymer diol constituting the soft segment of TPH, polyester diols, polyether diols, polyolefin diols, polylactone diols, and the like having a number average molecular weight of 500 to 10,00.0 are used.

Polyester diols include geltaric acid, adipic acid, succinic acid, speric acid, cepatic acid, oxalic acid,
Dibasic acids such as methyladipic acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, maleic acid, and fumaric acid, and ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and propylene glycol. , diethylene glycol, neopentyl glycol, etc. are used.

As the polyether diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. are used.

As the polyolefin diol, polybutadiene diol and the like are used, and as the polylactone diol, polycaprolactone diol and the like are used.

As the glycols and diamines constituting the hard segment of TPU, the diols shown as the raw materials for polyester diols, aliphatic and aromatic diamines such as ethylene diamine, propylene diamine, xylene diamine, etc. are used.

Examples of diisocyanates constituting the soft segment and hard segment of TPU include 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tri diisocyanate,
2.6-Dylene diisocyanate, 1.5-Naphthalene diisocyanate, xylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. are used alone or in combination of two or more. The TPU used in the present invention is as described above, but in order to obtain the desired thermoplastic resin, it is necessary to use a substantially organic It is necessary to dissolve it in a solvent.

As a TPU that is effective in the present invention, for example, Pandex T-5265 (trade name, manufactured by Dainippon Ink and Chemicals) (polyurethane consisting of adipic acid-based polyester diol and aliphatic diisocyanate: softening point: 53°C, bimolecular weight
120,000), bump yri, ;t, T-525(
Bandex T-5000 (softening point 155°C) and T-5 are insoluble in dimethylformamide and tetrahydrofuran (softening point 47°C) and MVC[, but soluble in dimethylformamide and tetrahydrofuran.
108 (softening point 160°C), T-R3080 (softening point 1
60℃), etc.

In the present invention, TPU starts polymerization in an amount of 3 to 200 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of MVC or MVC monomer at the time of charging.

TP for 100 parts by weight of MVC or MVC monomer
If the amount is less than 3 parts by weight of U, the coating using the resulting polymer will not have satisfactory flexibility, while if it exceeds 200 parts by weight, the cost will be high and it is economically unfavorable. Polymerizable phosphors include olefins such as ethylene and propylene, vinylidene halides such as vinylidene chloride, vinyl esters such as vinyl acetate, vinyl ethers such as n-butyl vinyl ether, butyl acrylate, and acrylic. Acid-
Examples include acrylic esters such as 2-ethylhexyl, methacrylic esters such as 2-ethylhexyl methacrylate, and the like.

The amount used is preferably 50% in the MVC monomer.
It is not more than 30% by weight, more preferably not more than 30% by weight.

This is because when the weight exceeds 50 fL, the heat resistance, durability, etc. of the resulting polymer deteriorate.

For the production of thermoplastic resins, a solution polymerization method using an organic solvent as a medium is used. Known organic solvents can be used in solution polymerization. For example, aromatic hydrocarbons such as toluene and xylene, ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone, ester compounds such as butyl acetate and ethyl acetate, tetrahydrofuran, dimethylformamide, etc. are used, and these may be used alone or in combination.

Among these organic solvents, tetrahydrofuran and dimethylformamide are particularly preferred from the viewpoint of solubility of TPU in the organic solvent.

The charging ratio of organic solvent/(TPU + MVC monomer) is 1/
1 to 3/1 is good. If the nucleation ratio is less than 1/1, polymerization tends to become unstable, and if the nucleation ratio exceeds 3/1, it is not economically advantageous.

The oil-soluble polymerization initiator used in solution polymerization may be any known polymerization initiator. Examples include azo compounds such as azobisisobutyloberonitrile, and organic peroxides such as lauryl peroxide, di-2-ethylhexyl peroxydicarbonate, and t-butyl peroxyvibarate. The amount used is based on the MVC monomer at the time of preparation.
It is about 0.01 to 2 weight.

The polymerization temperature is preferably 30 to 70°C, preferably 40 to 60°C. If the temperature is below 30°C, the polymerization rate tends to be slow, and if the temperature exceeds 70°C, the resulting polymer tends to have poor heat resistance, which is not preferred.

In the present invention, known chain transfer agents such as trichlorethylene and mercaptoethanol may be used.

According to the present invention, a thermoplastic resin useful as a paint, a fiber coating agent, an adhesive, etc. can be easily obtained, and the obtained thermoplastic resin has no problems of plasticity migration, exudation, and scattering, and It has good tensile strength, heat resistance and durability.

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 Polymerization was carried out using the polymerization recipe shown below. That is, raw materials other than vinyl chloride were charged into a stainless steel autoclave having an internal volume of 10 tons, the air inside was replaced with nitrogen, and then vinyl chloride was charged. A thermoplastic resin solution was obtained by reacting at 60° C. for 20 hours.

Reaction rate is 90%, TPU content in copolymer is 56wt%
Met.

Composition at time of preparation (parts by weight) TPU (Vandex T-5000) 50 Vinyl chloride 50 Tetrahydrofuran 200 G 2-Gobutsure\coconut 7L/ζFuseya cylinder total 1 book
0.05 Azobisisobutyronitrile
0.05 Next, the obtained thermoplastic resin solution was used to form a paint with the following composition.

Carbon black 3 parts by weight AC-186 (Ba, metal sizing agent, trade name manufactured by Adeka Argus) 1.5 1 Thermoplastic resin
50 1 Tetrahydrofuran
100 #Methyl ethyl ketone
50 liters of this composition was mixed for 8 hours in a horizontal motion type, completely closed ball mill (Dyno Mill, KDL type, manufactured by Wiley Kogyo Bakkofen) and passed through a vat to obtain a solvent-based paint.

The coating thickness after drying is 6011 m when the above paint is applied on a glass plate.
A casting film was obtained and evaluated.

The resulting coating film was tested in the following manner to evaluate its performance. The results are shown in Table-1.

Tensile test after heating: According to JIS K 6723, 1
After being kept at 00±2°C for 120 hours, a tensile test was conducted to determine the strength and elongation remaining.

Oil resistance test: Based on JIS K 6723, 2
After immersing in No. 1 insulating oil at room temperature for 1 week, the rate of change in weight is determined.

Comparative Example 1 In place of the thermoplastic resin of Example 1, vinyl chloride-vinyl acetate copolymer (Union Carbide Cor
p.

A paint was prepared and evaluated in the same manner except that 50 parts by weight of the product name (Vinylai) VMCH) and 15 parts by weight of dioctyl phthalate were used. The results are shown in Table-1.

Table 1 It can be seen that the coating film of Example 1 according to the present invention did not change its physical properties even after heating, whereas in Comparative Example 1, the plasticizer was scattered, making it hard and brittle. It is also found that the oil resistance of the present invention is excellent.

108

Claims (1)

[Claims] 1. Thermoplastic material that is soluble in organic solvents and has a softening point of 20°C or higher, relative to 100 parts by weight of a monomer mixture of a vinyl chloride drug or a vinyl chloride monomer and a monomer copolymerizable with it. A method for producing a thermoplastic resin 0, which comprises polymerizing the monomer or monomer mixture in the organic solvent in the presence of 3 to 200 parts by weight of polyurethane distomer.