JPH04183704A - Vinyl chloride copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer having excellent processability and having good Vicat softening temperature, impact strength and thermal stability by copolymerizing a specific allyl ester with vinyl chloride. CONSTITUTION:An allyl ester of formula I {R is-R1-(0R2)l-[R1 is (hydroxy) alkylene, phenylene; R2 is alkylene; l is 0, 1]; m is 2, 4, 5; n is 1-500} is copolymerized with vinyl chloride to obtain the objective copolymer comprising 0.01-50mol% of monomer units of formula II and 50-99.99mol% of monomer units based on the vinyl chloride and having a number-average mol.wt. of 20000-600000.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a vinyl chloride-based comonomer with excellent processability and a filtration method KI4 for the same.

[Prior art and the problem to be solved by the invention] PVC resins are widely used due to their excellent physical properties, but when the processing temperature is raised during molding, cyclized hydrogen is generated and the vinyl chloride resin decomposes. there's a possibility that. For this reason, vinyl chloride resin is said to be a W resin that is more difficult to mold than polyolefin. For this reason, many attempts have been made to improve the moldability of vinyl chloride resins.

The following method is known as a means for improving the moldability of vinyl chloride resin. For example, there is a method of lowering the degree of polymerization of vinyl chloride resin.

This method has the drawback that good moldability is obtained, but thermal stability and impact resistance are reduced. It is also known to improve moldability by blending a modified resin such as a low molecular weight methacrylic acid ester-styrene copolymer or an acrylonitrile-styrene copolymer with a vinyl chloride resin. However, in order to improve the workability of the molding part, K requires a large amount of modifier.

This method also has the disadvantage that the modified resin bleeds out during long-term use. Furthermore, there is a known method of copolymerizing vinyl chloride with α-olefins such as ethylene, propylene, butene, etc. to improve moldability, but the heat softening temperature decreases.
It has points.

On the other hand, compositions made by mixing vinyl chloride resin with a polymer plasticizer to give flexibility are used in automobiles.

Widely used in building materials, electrical, medical, etc. parts. For example, it is known to blend polymeric plasticizers such as poly-1-caprolactone with vinyl chloride to reduce fats; however, poly-ε-caprolactone that is simply blended has a chlorinated It is known that vinyl 4Ir exhibits a tendency to crystallize and loses flexibility and transparency over time. -1, JP-A-2-103
No. 212 discloses a porous polymer resin obtained by copolymerizing vinyl chloride and an acrylic acid ester of poly-ε-caprolactone. There is a problem in that the thermal stability of the fat decreases.

Therefore, it is desired to develop a vinyl chloride resin that has excellent moldability and is free from deterioration in physical properties such as thermal stability, impact resistance, softening temperature, and bleed-out upon cooling.

Steps to Solve the Problem] The present inventors have continued their intensive research in order to solve the above-mentioned problem. As a result, a vinyl chloride-based comonomer containing a specific proportion of monomer units based on allyl ester of polylactone has good moldability and thermal stability.

It was discovered that there was no deterioration in physical properties such as impact resistance and softening temperature, and there was no bleed-out, and the present invention was completed and proposed.

That is, the present invention is an integer of the general formula CI) CH20-R-0MoC(CH2+rO÷1HcI)l.

Contains a monomer unit α01 to 50 molar width represented by and a vinyl chloride-based monomer unit 50 to 99.99 molar width,
It is a vinyl chloride comonomer with a number average molecular weight of 20,000 to 600,000.

In the above general formula (1), R is represented by -R1-+OR2+T. Here, R1 is an alkylene group.

Hydroquine group or phenylene group, R2
is an alkylene group, and l! is 0 or l. The number of carbon atoms in the above-mentioned alkylene group and hydrothousalyl group is not particularly limited, but it is preferably 2 to 8 carbon atoms from the viewpoint of comonomability with vinyl chloride.

To specifically illustrate R in the above general formula CI), −+C
H2+F-1→CH2%, -+CH2%.

-+CH2%, -+CH,+r, →CTlz%
, +CHzk.

-CH2CHCH,CI(2--CH20CH2-.

H -CH2CH,OCH,CH,-,-CM,CHOCH
2CH.

CH3+ 1 m in formula [1) above may be 2, 4 or 5, but from the capacity S for synthesizing the allyl ester which is a heptad that gives the 1st position of the monomer shown in formula CI] , 3 is preferably 2 or 5. The allyl ester mixture in Figure 3 is solid.

In the formula (1) above, n is an integer from 1 to SOO. n
If it exceeds 500, the molecular weight of the macro-hetamine composed of allyl ester becomes large, resulting in a disadvantage that co-integration with vinyl chloride decreases.

The ratio of the monomer unit represented by the above-mentioned formula [) to the monomer unit based on vinyl chloride is such that the former is α01 to 50 mol%,
The latter should be 50-99.99 mol%, preferably the former 0.02-25 mol% and the latter 75-99.98 mol%. When the amount of the monomer state represented by formula CI) is small, the resulting jjllt,
The molding processability of the vinyl chloride co-monomer is insufficient, and too much reverse pressure significantly lowers the softening temperature of the resulting vinyl chloride co-monomer, which is unfavorable.

The cyclized vinyl copolymer of the present invention generally has a fine average molecular weight of 20,000 to 600,000. In particular, from the viewpoint of moldability, thermal stability, impact resistance, etc., the fine average molecular weight is preferably in the range of 30,000 to 200,000.

Furthermore, the j-mer units represented by formula CI) and the monomer units based on vinyl chloride are arranged randomly.

The vinyl chloride copolymer of the present invention can generally be suitably produced by the following method. That is, - Formula (n) CH2 = CHCH20 - R - 0 - E - C (CH 2 0 Horse H (II) 1 However, R41, -R1 - 4: 0R2 -i
(However, L and R1 are a method of copolymerizing the allyl ester shown in 1 with vinyl chloride.

The allyl ester represented by the general formula (II) used in the above method can be synthesized using the following allyl alcohol as a starting material. That is, CH2=CHCH
20 (CH2) 20H.

CH,=CHCH20(CH2)30H,CH,=CH
CH20(CH,)40H, CH,=CHCH20(C
H2), OH.

CM2=CHCH, 0(CH2)60H, CH2=CH
CH20(CH,), OH, CH,=CHCH20CR
It can be obtained by combining β-10 Viola Wattone, δ-Valero Waton, or 6-Caproluftone in the presence of one or more allylic alcohols such as 2CH200H, OH, =CHCH2QC6H40H.

The combination of vinyl chloride and the allyl ester represented by the above formula [■] is 1 ml of suspension, 1 ml of solution, 1 ml of bulk,
It can be carried out by either emulsion polymerization or precipitation polymerization.

Regarding suspension polymerization, which is one of the preferred polymerization methods, the following describes
Let's be specific.

In suspension polymerization, in the presence of an aqueous medium and an oil-soluble polymerization initiator,
The radical combination of the allyl ester and vinyl chloride represented by formula (n) is the combination of the ester and vinyl chloride.
As mentioned above, the coalescence ratio is 0.01 to 50 mol% for the former.
The latter is in the range of 50 to 99.99 mol%.

Monomers known as vinyl chloride and polymerizable polymers other than the allyl ester represented by formula (II), i.e.,
Ethylene, propylene.

Puden, heptene, acrylic acid, methacrylic powder, methyl acrylate, ethyl acrylate.

Butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. may be added to the vinyl chloride copolymer of the present invention within the range that does not essentially change the physical properties of the vinyl chloride copolymer of the present invention, for example, O, It is also possible to combine in the range of 1 to 5 molar arcs.

The m of the aqueous medium is suitably 0.5 to 3 times the volume of the mixture of vinyl chloride and a monomer such as allyl ester represented by formula (II) above.

Examples of oil-soluble polymerization initiators include lauryl peroxide and benzoyl peroxide.

Diisoprobyl peroxydicarbonate.

G11ee-Butyl peroxycarbonate.

G 2- Ethyl 1,000 Silver O 1,000 Dicarbo 4-)+
X;-2-x) 1,000 ethyl carbonate, 2-methoxydicarbonate, 2-methoxydicarbonate)
, TSR
t-butylpa-o-1,7-butylpa-o-so-dicarbonate, di-3-metho-butylpa-o, di-4-t@rt
- Butyruncrohehira silver ozen dicarbohydrate, azobisisobutyronitrile, 2° 2-7 zodox 2.4
- dimethylvaleronitrile, 2. Any known radical polymerization initiator may be used, such as 2'-azobis-2,4-dimethothenonevaleronitrile and acetylcyclohequine sulfate, and these may be used alone or in combination. The amount of the oil-soluble polymerization initiator to be used is preferably at α001 to α001 to 23 with respect to 100 parts by weight of the mixture in the fired body.

For suspension polymerization, dispersants are generally used.

Dispersants include partially saponified polyvinyl acetate, methyl cellulose, meth-1000 diethyl cellulose, and hydroquine ethyl cell p.
Any known dispersing agent may be used, such as -sugar, hydrochloric acid cellulose, etc. In addition, a nonionic surfactant such as polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, etc. may be used in combination. Yo℃・.

The total amount of these dispersants and surfactants used is preferably 0.01 to 311 parts based on coulometric parts of the monomer warm mixture Zoo.

Although there is no particular restriction on the order in which the substrates for the first reaction described above are added, it is preferable that the allyl ester of formula Cn) and the vinyl chloride are uniformly dissolved in each other before starting the first reaction. For this purpose, methods such as preliminary stirring before the start of polymerization, post-addition of a polymerization initiator, and separate preparation of a mixed solution of the allyl ester of formula [■] and vinyl chloride may be selected as appropriate.

1. The moisture content may be any temperature at which the oil-soluble polymerization initiator thermally decomposes, but numerically preferred is 30 to 80°C. A known chain transfer agent comprising a chlorine-based compound such as a chlorine-based compound, a disulfide-based compound, or trichlorethylene, or a solvent that dissolves the allyl ester of formula (II), such as hexane, pentane, or heptane, may be added.

Known methods and conditions for one-money production and one-go conditions should be adopted without restriction.

After drying, the vinyl chloride-based comonomer produced by the 1-polymerization can be put to practical use as it is.

[Action and effect]

To specifically explain the effects of the vinyl chloride comonomer of the present invention as described above, first, regarding processing fluidity,
Allyl ester of poly-ε-caprolactone is 0.11
A vinyl chloride based copolymer having a number average molecular weight of 60.000 introduced in a molar ratio is superior to a vinyl chloride monopolymer having a number average molecular weight of 143.000. In addition, the number average molecular weight of Vicat softening temperature, impact strength, and thermal stability is 43.0.
Superior to 00 vinyl chloride polymer.

The reason for this favorable [2) Ili engineering dynamics is not clear at present, but the above formula [2] as a comonomer is not clear at present.
This is thought to be because copolymerizing the allyl ester represented by II) with vinyl chloride lowers the molecular interlocking force of the vinyl chloride copolymer.

The vinyl chloride-based comonomer of the present invention has excellent processing fluidity, Vicat softening temperature, impact strength, and thermal stability.
Since it contains polylactone in the side chain, it has excellent flexibility and transparency, and can be used for rare applications by injection molding or extrusion molding. It is possible to use For example, pipe fittings, OA equipment hedging.

Hard parts such as window frames, or soft films.

sort. Any soft material such as a base, tube, or j-sket can be used.

Implementation In an autoclave with a volume of @51, distilled water 21, *([J[
s% polyvinyl acetate 31% tort-butyl peroxide) LOg, number average molecular weight 7,900 (
Poly-4- of the above-n = 68 in formula (II)
20 (l) of allyl ester of caprolactone and 800 g of vinyl chloride were charged, and 1 cup was carried out at 60°C for 5 hours. The 1 cup ratio of vinyl chloride was 68's.

By passing the product through the mouth and drying it, uniform white fine particles were obtained. The number average molecular weight (Mn) of this co-monomer was measured in terms of standard polystyrene, and was found to be 48,00.
It was 0. Further, this co-monomer was purified by precipitation using tetrahydro 7 run and acetonitrile. A part of this monomer was formed into a film, and its infrared absorption spectrum was measured. The results are shown in FIG. From this, the stretching vibration of C-H is around 3.000 ex-', and the stretching vibration of C=O is around 1
,720cm-1K, C-CZ expansion/contraction lift is 600~7
It was found that it exists in 00 countries-1. Results of measuring IH-Nuclear Magnetic Resonance Spectrum (H-NMR) 1
As shown in the km2 diagram, it was found to be based on the following spectrum.

H-NMR integral curves of polyvinyl chloride and poly-1-caprolactone show that 115 wt' IG ((112 moles) of allyl ester of poly-caglolactone is present in this polyvinyl chloride copolymer). I found out that it is.

Implementation @2-14 Easy 5! 2j of distilled water in an autoclave.

-Polyvinyl acetate 3# with a chemical degree of 75, t-rt-butylpero-oxcineodecanoate 19, polyvinyl chloride of various molecular weights, allyl ester of Kag tetralactone and vinyl chloride were prepared, and under the conditions shown in Table 1, 1 We held a meeting. Thereafter, the product was passed through the mouth and dried to obtain uniform white fine particles. The molecular weight of this polymer was measured by the same method as in Example 1. These results are shown in Table 1.

Example 15 Distilled water 2/2 to a capacity 51 eid crepe.

- Polyvinyl acetate with a degree of 75 3. jij, t@rt-
petil meo neodecanoate 1y1CH2=CH
CH20Cf (, CHCH20 (-C(CH2) No. 20 H CI & average molecular weight 332.n = 3) 3009 and vinyl chloride 700g were charged and polymerized at 60°C for 5 hours. The 1 ratio of vinyl chloride was 63. By passing the product through the mouth and drying it, uniform white fine particles were obtained.Furthermore, a part of this copolymer was precipitated from tetrahydro7ran and acetonitrile. 11 was made into a film and its infrared!!@ absorption spectrum was measured, and the result was -0
-H stretching vibration is 3.200~A600cIK-'K,
The stretching vibration of C-H is around 3.000°, the stretching vibration of C=O is around 1720°, and the stretching vibration of C-CJ is around 6.
It was found to exist between 00 and 700 tx-1. In addition, from elemental analysis of this co-mono-coalescence, β-10
Piolawaton's allyl ester is 23.611i1 (
7.1 mol%) was found to be copolymerized. In addition,
The number average molecular weight of this co-merged is 4!41,000 (GP
Standard polystyrene equivalent according to CK).

Example 16 2/2 of distilled water in an autoclave with a capacity of 51.

Polyvinyl acetate 32 with saponification degree of 75%, tart-butyl barodecanoate tg, CH2=CHC)1
20CI(2CH,0(-C(CH2)40÷yo(number average molecular weight 1,100.n=10) 200y and 800g of vinyl chloride were charged and polymerized at 60°C for 5 hours.The co-1 ratio of vinyl chloride was The product was passed through the mouth and dried to obtain uniform white fine particles.Furthermore, a part of this copolymer was purified by precipitation from tetrahydrofuran and acetonitrile. As a result of making a part of the body into a film and measuring its infrared absorption vector, the stretching vibration of -〇-H is 3.200 to 3.600α-"K, and the stretching vibration of C-H is 3.OOOtx-" Nearby, the stretching vibration of C=0 is 1,720 m-1, and the stretching vibration of C-Cl is 6
00 to 70012-1. Further, by elemental analysis of this co-mono-merite, it was found that 111% by weight (111 mol%) of the allyl ester of δ-valerolactone was co-co-mono-coal. The fine average molecular weight of this co-monomer was 44.000 (based on standard polystyrene by CGPC).

Examples 17 to 32 Physical properties of the vinyl chloride copolymers produced in Examples 1 to 16 were evaluated as follows. The results are shown in Table 2.

(1) Preparation of sheet by hot roll 100 parts by weight of vinyl chloride comonomer K, butyl tin malate stabilizer (
Nitto Kasei Kyoku TVS-N-2000E) 4 parts by weight was added, and this was kneaded for 5 minutes with a heated roll at 160°C.
A rolled sheet having a thickness of 1.1 mm was prepared.

(2) Cut the roll sheet of (υ) into a pellet shape of approximately 3 inclines, and use a Koka type flow tester to test it using the constant temperature method (180°C).
) Fluidity was evaluated by K.

(3) Cut the roll sheet of (1) into 4 x 21 squares, use an open cutter, and pass it to JIS-7212.
Thermal stability at 190°C was evaluated.

(4) Four rolled sheets of (1) were rolled up and hot pressed (180°C, 50%) for 7 minutes to produce a pressed sheet with a thickness of 4 m. The impact resistance was evaluated using a Nyarhi impact test piece based on JIS-7111 from the press sheet.

(5) A 15 m square test piece was made from the 4 m thick press sheet prepared in (4) and measured in accordance with JIS-7206. The softening temperature was measured.

(6) An 11-sided test piece was made from the 4wm thick press sheet prepared in (4), sandwiched between sheets of polystyrene and acrylonitrile-butadiene-styrene copolymer (ABS), and subjected to a load of 3009 for 70 minutes. It was left at ℃ for 5 days and tested for migration. Changes in the surface conditions of the polystyrene and ABS sheets were visually observed and evaluated using the following criteria.

○: No change at all Δ: Very slight cloudiness ×: White cloudiness υ] After the test piece used in the test (6) was left for 3 months, changes in transparency were visually observed and evaluated according to the following criteria.

○: No change at all Δ: Transparency decreases somewhat X:　a Clarity decreased considerably Comparative examples 1 to 5 2/2 of distilled water in an autoclave with a capacity of 51.

3jl of polyvinyl acetate with a m degree of 75%, t@rt-butylperoxine neodecanoate) 1#.

Ester of poly-ε-caprolactone and hydroxyethyl methyl methacrylate (number average molecular weight 800) 50
．． P and 950 g of vinyl chloride were charged and polymerized at 60°C for 5 hours. Thereafter, the product was passed through the mouth and dried to obtain the copolymer of Comparative Example CI) as uniform white fine particles. The number average molecular weight of this co-monomer was 52,000.

Furthermore, a vinyl chloride monopolymer (
2) (! average number of molecules 43,000) and (3) (i
1 average molecular weight 61,000) was synthesized.

A combination of these (1), (2) and [3] was prepared in Example 17
A roll sheet and a press sheet were prepared in the same manner as in ~32, the physical properties of each were measured, and these were compared e'1
It was set at 11-3.

Furthermore, to 100 parts by weight of a combination of [2] and [3], 1 part of polycaprolactone (average molecular weight 7100 in 1) was added.
0 parts by weight were kneaded and evaluated in the same manner as Examples 17 to 32, and are also listed in 12 as Comparative Examples 4 and 5.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 respectively show an infrared absorption spectrum and a 1H-nuclear magnetic resonance spectrum of the vinyl chloride base yarn 1 union obtained in Example 1.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. l is 0 or 1
It is. ) and m is 2, 4 or 5, and n is 1 to 5
It is an integer of 00. ] Contains 0.01 to 50 mol% of monomer units represented by and 50 to 99.99 mol% of monomer units based on vinyl chloride,
A vinyl chloride copolymer having a number average molecular weight of 20,000 to 600,000. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R is -R_1■OR_2■ (However, R_1 is an alkylene group, hydroxyalkylene group, or phenylene group, R_2 is an alkylene group, l is 0 or 1
It is. ), m is 2, 4 or 5, and n is 1 to
It is an integer of 500. ] A method for producing a vinyl chloride copolymer according to claim 1, which comprises copolymerizing an allyl ester represented by the following formula with vinyl chloride.