JPS6142519A - Production of vinyl chloride copolymer - Google Patents

Abstract

PURPOSE:To produce the titled copolymer improved in surface properties and low-temperature properties, by radical-copolymerizing a vinyl chloride monomer with a polymerizable unsaturated organosilicon compound and other polymerizable monomers. CONSTITUTION:50-99.99pst.wt. vinyl chloride monomer is radical-copolymerized with 0.01-50pts.wt. polymerizable unsaturated organosilicon compound of formula I or II (wherein Vi is vinyl, Me is methyl, Ph is phenyl, m is 0 or a positive integer and n is a positive integer) or a like formula, and 0-49.99pts.wt. other polymerizable monomers (e.g., acrylonitrile) at 30-120 deg.C for 1-30hr in the presence of a polymerization initiator.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a method for producing an improved vinyl chloride copolymer, and in particular, to a method for producing an improved vinyl chloride copolymer, which has excellent thermal properties (heat resistance), surface properties, and mechanical properties. The purpose is to provide vinyl chloride copolymers.

(Prior art) Regarding the modification of vinyl chloride resin, silicone (oil,
Many attempts have been made to add and blend silicone vinyl chloride resins, etc., and most of them have focused on modifying the surface properties of vinyl chloride resins by adding them to silicone vinyl chloride resins.

For example, in Japanese Patent Publication No. 5B-35537.

By adding 0.2 to 7% silicone to vinyl chloride resin, the amount of plasticizer extracted into the SL, 8 aqueous solution can be reduced. It has been disclosed that an agricultural PVC film with excellent fog resistance can be obtained by combining the addition of ~0.02 PHH with an antifogging agent, and more generally, by adding silicone oil to the resin, It is known that improved resin fluidity, improved s-type properties, and imparted surface lubricity can be achieved.

However, the affinity between vinyl chloride resin and silicone is extremely poor, and due to the slipperiness of silicone itself, C
2.It is easy to slip and is difficult to sufficiently disperse even if the amount of silicone is small. For this reason, the special public official 58-3553
Publication No. 7 C describes the use of an emulsifying compound of a plasticizer and silicone to improve the dispersibility with the resin.

However, even if such a method is used, there is a limit to the amount of silicone added; for example, if more than 10 tN% is added, sufficient dispersion will not be achieved and bleeding will be severe due to poor affinity.

On the other hand, various attempts have been made to improve the affinity for vinyl chloride resins by modifying silicone itself (Japanese Unexamined Patent Publication No. 55-91663, No. 57-12070).
Although such attempts are extremely effective for specific applications I, they are not necessarily sufficient for other applications.

On the other hand, silicone has particularly excellent thermal properties (heat resistance, low-temperature properties, etc.), and therefore, in addition to improving the surface properties mentioned above, it is also possible to improve the thermal properties of the entire resin by combining silicones. However, no technology to be considered has been proposed so far.

C) Structure of the Invention) The inventors of the present invention have completed the present invention under these technical problems (:) through intensive research. Namely, 1. The present invention is based on (a) polyvinyl chloride mono(material) 50 to 99.99 Weight part.

c) Polymerizable unsaturated organosilicon compound 0.01-50
Parts by weight, c/S) Other polymerizable monomers 0 to 49.99 parts by weight.

Method C for producing a vinyl chloride copolymer characterized by radical copolymerization of
The advantage is that a vinyl chloride copolymer with improved overall resin thermal properties, particularly low-temperature properties, can be easily obtained.

The present invention will be described in detail below. In the present invention, (a) (0) is copolymerized with a vinyl chloride monomer. Examples of synthetic unsaturated organosilicon compounds include the following. However, in the following @Me
represents a methyl group, ph represents a phenyl group, and vl represents a vinyl group.

Cylochitin (1): vl-si (ost Me3) 3 Cylochitin (2): Me (Vl-8iO).

Xylochitin (3): n: 0 or a positive integer Xylochitin (4): m: 0 or a positive integer n: A positive integer Xylochitin (5): m: 0 or a positive integer n: A positive integer Xylochitin (6) : IJr+ CtH2=O-Coo(1,H,-8i(O8iMe,
).

Siloxane (7): O8iMe, O8IMe.

I R-8t-Q-6i-R +　　　　　　　　　　1 0S10Si 0StMe.

Me R: -C3H,00CO=cH2 Xylochitin (8): R: Same as above, n: 0 or positive integer Xylochitin (9
): Me Me Ms + 1 1kl
e M e R: Same as above Siloxane (10): Siloxane (11): R-81r (O8iMez)n 08i)Je3)
sR: Same as above, n: positive integer xylochitin (12): OMe Ph xylochitin (13): OMe Me xylochitin (14): n: 0 or positive integer xylochitin (15): R OH2=CH-cH2ocH2cacH,oc ,H,s
t (ostye3)3 siloxane (16): m, n: positive integer siloxane (17): [1-CI+-0-C,H,81(O8iMQ,)3? 0H2-C-C-0-Cs I(g S x (081
Me3) 3siloxane (19): Q-81 ((0811Je2)n081Mes) 3゜n=positive integer Siloxane (20): p'-cH2C! J(, aH2si (Me) (08
1Me,) 2R': -0CR,CHCjH,-0
0-Cj=CH2silochitin (21): Used if necessary (Q other monomers 7,
α-olefin, vinyl ether, acrylic ester,
Examples include vinyl ester, methacrylic ester, maleic ester, fumaric ester, allyl ester, allyl ether, styrene, acrylonitrile, and vinylidene chloride.

The copolymerization of each of the monomers that are component (a), component (b), and component Ql) described above is carried out in the presence of a radical polymerization initiator using method C: copolymerization. The polymerization initiator to be used may be a polymerization catalyst that is conventionally used for polymerization of vinyl chloride or a monomer mixture mainly composed of vinyl chloride (suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization, etc.). Any catalyst may be used, for example, an organic peroxide catalyst, an azo compound catalyst, a redox catalyst, and the like.

The polymerization reaction can be carried out by methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. For example, when performing suspension polymerization, it is sufficient to follow the usual method of M-turbid polymerization of vinyl chloride using a polymerization initiator such as an organic peroxide, and the polymerization temperature and time are approximately 30 to 120°C.
One polymerization time may be 1 to 30 hours. (b) Organosilicon compounds and other single R component components used as needed (seaweed) can be charged into the polymerization vessel either by charging them from the beginning of the entire company or by charging them until a polymerization rate of 50% is reached (two-sequential). Any method of addition (adding in several portions or adding continuously) may be used.

According to method 12 of the present invention, vinyl chloride monomer 50 to 99.
By copolymerizing at a ratio of 0.01 to 50 parts of a polymerizable unsaturated organosilicon compound to 1 part of 99 frl, and 0 to 49.99 parts of another polymerizable monomer. , a copolymer can be obtained that has both the physical and chemical properties inherent to vinyl chloride resin and the properties possessed by organosilicon compounds.

Next, specific examples will be given, but the present invention is not limited thereto.

Example 1 Internal volume 50! Pure water 30KP in a stainless steel polymerization vessel,
Partially saponified polyvinyl alcohol 20f.

The following monomer mixture 1. II or 1 (approximately 15) I/
).

And di-2-ethyl rubber oxydicarbonate (7.5P) was charged as a polymerization initiator.

The mixture was stirred and kept at room temperature for 20 hours at 52°C. The contents are removed, dehydrated and dried to remove the vinyl chloride copolymer.

Monomer mixture ■ Vinyl chloride 1217 Shaki Nan! 61 3 KP Siloxane 17) 30 P Siloxane (3) (
However, n=40>20? Monomer mixture vinyl chloride 13.5 sand siloxane (il 1.511 siloxane (11) (n-6) monomer mixture vinyl chloride 14.7Kf siloxane (6)
J 0.3 IF Nrochitin (5115
F (however, m=300.n=10) For each copolymer thus obtained, JISK 62
The average degree of polymerization was measured according to 71, and 35 parts by weight of di-2-ethylhexyl phthalate, 1.0 parts by weight of dioctyltin mercaptide, 1.0 parts by weight of calcium stearate, and 1 part by weight of di-2-ethylhexyl phthalate, 1.0 parts by weight of calcium stearate, and 1 part by weight of 100 m' of this copolymer. 0.3 m part of wax was blended and kneaded for 10 minutes at 160°C using a 6-inch roll. Next, add this mixer to 1
Press molded at 70℃ to make a sheet, JI8K6
745, the change in rigidity modulus due to temperature C2 was measured, and the activation energy of the flexibility temperature and rigidity modulus was determined. The results were as shown in Table 1. Note that Table C; is the same as the commercially available Boli vinyl chloride (average degree of polymerization 1300).
The test results are also listed.

From the results shown in Table 1, it can be seen that the copolymer according to the present invention has excellent flexibility at low temperatures and shows little change in flexibility due to temperature.

Example 2 Internal volume 50! Stainless steel polymerized IC1 pure water 30KP1
Partially saponified polyvinyl alcohol 20j', the following monomer mixture Iv or V (approximately 15%), and di-2-ethylhexyl silver oxydicarbonate (7.5jF-) as a polymerization initiator were charged.

The temperature was raised while stirring, and the copolymerization reaction was carried out at 58° C. for 20 hours. The contents were taken out, dehydrated and dried to obtain a vinyl chloride copolymer.

Monomer mixture ■ Vinyl chloride 15? Cylochitin (311 mM (however, n = 40) > Monomer mixture V - Vinyl chloride 13.5 My Cylochitin (3) 150 P (however, n-density 40) The average degree of polymerization was measured for each of the obtained copolymers, and the Example 1 (same recipe) to make a sheet with a thickness of 1 m, and this was made into a 2.5 cm x 10 cm J
Two cuts were made. These two sheets were stacked together and a load of 500P was applied to the whole, and after being compressed at 60°C for 24 hours, the force of peeling between the sheets was measured (blocking property test).The results are shown in Table 2. .

From the results in Table 2, it can be seen that blocking occurs in the case of the copolymer according to the present invention.

Example 3 Three types of copolymers were prepared by adding the following ingredients to a stainless steel polymerization vessel with an internal volume of 2 mm (C: charging 1: changing only the polymerization initiator).

Copolymer F: lauroyl peroxide was used, and the polymerization temperature was 85°C.

Copolymer G: lauroyl peroxide was used, and the polymerization temperature was 67°C.

Copolymer H di-2-ethylhexyl peroxydicarbonate was used, and the polymerization temperature was 58°C.

(M combined preparation) Pure water 1000j' Vinyl chloride 475? Silochitin (6124Ji' Partially saponified polyvinylalcohol 0.71 Cole initiator 0.25 ?Each copolymer F,
The average degree of polymerization was measured for G and H, and 100 parts by weight of each of C; 3! for dibutyltin mercaptide. 1 part of calcium stearate and 1 part by weight of calcium stearate were mixed and kneaded for 10 minutes using a 6-inch roll. However, for copolymer F, the roll temperature was 160°C, and for copolymers G and H, the roll temperature was 180°C.

Next, this roll v-1 was coated with copolymer FI: 1
at 70°C and 190°C for copolymers G and H.
Each was press-molded. These sheets and similarly molded commercially available polyvinyl chloride/I/ (PVC, sheets with an average degree of polymerization of 400, 700, and 10001)
Charpy impact test according to I8K 6745, JIB
The K 6723 C quasi-embrittlement temperature was measured. On the other hand, the fluidity of each polymer roll sheet was examined using a Koka type flow tester under the conditions of IJ I 50 Mylty&. The results were as shown in Table 3.

Table 3 (drops) Temperatures showing the flow of 2 x 16-" d,/mm As can be seen from Table 3, copolymers F, G and H each have a lower temperature than commercially available pva with a corresponding average degree of polymerization of 1-" Ding” 1. Example 4 Copolymer resin in Example 2 I and E, Example 3 (=
Copolymer F, C1-M, Nibi H2 City Hpva (
For the above-mentioned 3 persimmons), roll FIN, knead, and press-form with the same recipe as in Example 3 to make a notebook. The friction coefficient was measured.

The results were as follows, Static friction coefficient copolymer DO,23~0,24ttE
O, 2: (~024# F O
,21~0.23 () 0.21~0.
23 copolymer HO, 21~0.23 pvctp4oo+ 0.24~o2hPVOt
P7001 0.24-0.2tipvc+p
1000) 0.25 to 0.27 As described above, the copolymer DH has a small coefficient of static friction, making it difficult for molded products C' to stick to molded products, thereby improving quality.

Patent applicant: Shin-Etsu Chemical Ede Co., Ltd. Procedural amendment August 318, 1982 1. Indication of the case Patent Application No. 164550 of 1982 2. Name of the invention Process for producing vinyl chloride copolymer 3. Person making the amendment 4. Agent Address: 4-9-6, Nihonbashi Honmachi, Chuo-ku, Tokyo 103, Subject of amendment 1) The chemical formula on page 11, line 5 of the specification is as follows: C
Make two corrections.

" ” that's all

Claims (1)

[Claims] 1. (a) 50 to 99.99 parts by weight of vinyl chloride monomer;
(b) Vinyl chloride characterized by radical copolymerization of 0.01 to 50 parts by weight of a polymerizable unsaturated organosilicon compound, and (c) 0 to 49.99 parts by weight of another polymerizable monomer. Method for producing copolymer