JPS60365B2 - Production method of poly(-N-ethylene trimerite imide) resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel resin, and more particularly to a method for producing a polyfN-ethylene trimellitate timide (hereinafter abbreviated as PETI) resin consisting essentially of repeating units. This invention relates to a method for producing a resin with excellent melting properties, impact resistance, etc. by blending an organic polysiloxane resin during polymerization or into the polymer.

Fibers, films, or molded products obtained from PETI have high melting points and glass transition points, and also have excellent mechanical properties such as strength and modulus of elasticity, and chemical resistance. It is expected to be used as tire cords, electrically insulating thin film materials, magnetic tape, etc.

However, since PETI has a high glass transition point and a high melting point, it has the disadvantage that the viscosity of the molten state becomes extremely high.

Therefore, when producing PETI by the melt polymerization method, (i
) Puts a significant load on the frame motor, (ii) It is difficult to control the polymer temperature due to the internal heat generation of the polymer due to the lampshade, when taking out the side polymer from the polymerization can.
Problems such as a large amount of can residue occur. Furthermore, during melt spinning and melt film forming, (i) a significant load is placed on the extruder and gear pump, (ii) the filter pressure increases, making it impossible to obtain a sufficient discharge amount, resulting in a decrease in productivity;
D has disadvantages such as the discharge amount tends to fluctuate and it is difficult to obtain uniform threads or films. In order to improve these points, the present inventors have arrived at the present invention as a result of intensive research.

That is, the present invention involves adding 0.01 to 10% by weight of an organic polysiloxane resin during the polymerization of a poly(fN-ethylene trimellitate imide) resin consisting essentially of the repeating unit (1) of the following formula, or to the polymer. A method for producing poly(fN-ethylene trimellitate imide) based resin by blending
It is. The present invention will be explained in more detail below.

PETI used in the present invention has the general formula (0) [however, R
(1}Hydrogen, ■C, ~C2o alkyl group (including those in which one hydrogen atom of the alkyl group is substituted with a benzene nucleus or a hydroxyl group) and/or {3}phenyl group (1) n is a real number of 1 or more (the average value does not necessarily have to be an integer,
n=1)] in the presence of a transesterification catalyst or a polycondensation catalyst that is usually used in the production of polyester.

Its intrinsic viscosity is 0.281/g (phenol/sym-
Use one having a weight ratio of 3,000 or more in tetrachloroethane 6/4 (weight ratio). In the present invention, PET
I is a shellfish to the extent that it does not substantially impair the excellent properties of PETI.
At least 80 mol% of the repeating unit of the general formula (1)
or more (preferably 90 mol% or more, particularly preferably 95 mol% or more)
homopolymers and copolymers containing (mol% or more). In the case of a copolymer, the copolymerization component is a compound copolymerizable with formula (0), such as amino acids (for example, amino acids such as aminohexanoic acid, aminobenzoic acid, etc.), lactams (for example, '-caprolactam, etc.), and lactones. (For example, 8
-propiolactone, '-caprolactone, etc.), oxycarboxylic acids (e.g. salicylic acid, glycolic acid, etc.),
These include half-esters of dicarboxylic acids and glycols.
According to research by the present inventors, when PETI is used as a fiber, it has an intrinsic viscosity of at least 0.2 to 1/g (preferably 0. to 1/g or more), and when used as a molded article, 0. phantom 1/g or more (preferably 0.3 mother 1/g
or above), and when used as a film, excellent properties cannot be obtained unless the film has an intrinsic viscosity of 0.3 dl/g or more (preferably 0.4 dl/g or more).

In addition, the PETI of the present invention contains stabilizers such as phosphoric acid, phosphorous acid, their esters, and metal salts, matting agents such as titanium dioxide, lubricants such as particulate silica clay, and further antioxidants and plasticizers. , antistatic agents, dyes, pigments, ultraviolet absorbers, and reinforcing agents such as carbon black, carbon fibers, glass fibers, and synthetic fibers.

It may also contain other polymers, such as polyester, nylon, polyolefin, polysulfone, polyphenylene oxide, polystyrene, thermoplastic fluorine-based polymer, etc., within a range that does not impair its properties. Also, P of the present invention
ETI also includes cases where the terminal groups of hydroxyl groups and carboxyl groups are partially or completely blocked.

The organic polysiloxane resin used in the present invention has the formula (m) (where R, , R2, and R3 are the same or different aliphatic hydrocarbon groups or aromatic hydrocarbon groups, and n is Representative examples include organic polysiloxanes represented by the formula (an integer having an average value of 0 to 3,000), random and/or block polyalkylene oxide polysiloxanes containing structural units, polyesters, polysiloxanes, and the like.

Specific examples of organic polysiloxanes include dimethylpolysiloxane, methylethylpolysiloxane, phenylmethylpolysiloxane, and methylbutylpolysiloxane. The amount of organic polysiloxane resin added is 0.01 to 1% by weight based on the total amount of resin, preferably 0.01 to 1% by weight.
5% by weight, and for specific purposes 0.1-2. weight% of
It is.

If the amount of the organic polysiloxane resin is less than 0.01% by weight, the effect of lowering the melt viscosity, which is the objective of the present invention, will not be sufficiently expressed, and if it exceeds 1% by weight, the physical properties inherent to PETI will deteriorate, which is not preferable. .

In the present invention, there are no particular restrictions on the blending (timing and method) of the organopolysiloxane resin into PETI, but preferably during PETI production, especially when the intrinsic viscosity is 0.1.
It is preferable to mix it before reaching 1/g of PET.
It is also customary to incorporate it into the monomers forming I.

Any known method may be used for blending PETI with the organic polysiloxane resin. An organic polysiloxane resin may be added to PETI, mixed in a mixer, kneader, etc., and then directly molded, or alternatively, it may be mixed in a molten state in an extruder, etc., formed into chips, and then molded. The polymer obtained by the method of the present invention can be used in fibers, fibrous molded products such as woven fabrics and non-woven fabrics, membranous molded products such as films and sheets, deep-drawn containers,
Can be used as hollow molded products such as bottles, tubes, and pipes.

The present invention will be explained below with reference to Examples, but is not limited thereto. Example 1 Nf hydroxyethyl) trimellitic acid imide 28. Arm, methylphenylpolysiloxane (KF54, manufactured by Shin-Etsu Chemical Co., Ltd., silicone oil) 0.11 base, titanyl hydroxyate potassium dihydrate 3. Pour mg of mouse into a glass container with a ratio of 10 C equipped with a distillation device and a feeding device, melt it at 22,000 ℃ in a nitrogen stream, then keep it at the same temperature for 1 hour and 2,500,030 minutes to react and collect the produced water outside the system. I left.

Then, the pressure was gradually reduced and maintained at 2 Yanagi Hg, and polycondensation reactions were carried out at 25,000 for 30 minutes, at 260oo for 30 minutes, at 27,000 for 30 minutes, at 28,000 for 20 minutes, and at 2,900○ for 2 minutes. After quenching, a pale yellow polymer was obtained. The intrinsic viscosity after pulverization and drying was 0.44 dishes/g. Example 2 0.118g of dimethylpolysiloxane (KF96: manufactured by Shin-Etsu Chemical Co., Ltd., silicone oil) was used instead of methylphenylpolysiloxane in Example 1, and the same conditions were used for 20 minutes at 290002 Hg in Example 1. The polycondensation reaction was carried out for 56 minutes, and the intrinsic viscosity was 0.40 Ml/g.
A brown polymer was obtained.

Example 3 The melt viscosity of the polymers obtained in Examples 1 and 2 at 29,000 ml was measured using a Koka type flow tester.

Claims (1)

[Claims] 1 Poly-(N-ethylene trimellitate imide) consisting of a repeating unit (I) substantially of the following formula ▲ Numerical formula, chemical formula, table, etc. ▼
A method for producing a poly(N-ethylene trimellitate imide) resin, which comprises blending 0.01 to 10% by weight of an organic polysiloxane resin during polymerization of the resin or into the polymer.