JPS5840582B2 - Halogen-containing resin stabilizing composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a halogen-containing resin stabilizing composition containing a novel functionalized organotin compound.

Various dialkyltin derivatives are widely used as excellent stabilizers for halogen-containing resins.

The present invention provides a novel stabilizer that is superior to dialkyltin stabilizers in imparting thermal stability to halogen-containing resins and compatibility with the resins.

Furthermore, it is a halogen-containing resin stabilizing composition that significantly reduces unpleasant odors generated during processing of conventional halogen-containing resins containing dialkyltin mercaptide.

That is, the present invention provides halogen-containing resins with the general formula % formula %) [wherein R is an alkyl group having 1 to 18 carbon atoms, and Y is a group -8(CH2)nC0OR', -SR'-
0OCR' or -00CCH=CHC0OR' (R
' is an alkyl group having 1 to 18 carbon atoms, an alkenyl group, a cycloalkyl group, a benzyl group.

is an integer of 1 to 4), z is a group -8-, -8m-.

-8(CH2)ncOo- or -00CCH=CHCO
A halogen-containing resin stabilizing composition characterized by containing one or more organic tin compounds having a functional group represented by O- (m and n are integers of 1 to 4). It is.

The organotin compound having a functional group represented by the above general formula is derived from a raw material of bis(alkoxycarbonylmethyl)tin cybaride or bis(alkoxycarbonylmethyl)tin oxide by a conventional dehalogenation reaction or dehydration reaction.

Bis(alkoxycarbonylmethyl)tin cybaride is, for example, J, Org, Chem, 16, 466.
-75 (1951), and when it is hydrolyzed, it becomes an oxide.

Examples of the R group in the organic group -CH2COOR having a functional group include linear and branched alkyl groups such as methyl, ethyl, propyl, butyl, aryl, hexyl, octyl, and dodecyl groups.

Further, in Y in the above general formula, the R' group includes, for example, methyl, ethyl, propyl, butyl, □al, hexyl,
Alkyl groups such as octyl, dodecyl, octadecyl,
methoxyethyl, butoxyethyl, octoxyethyl,
Examples include substituted alkyl groups such as methoxyethoxyethyl and methoxybutyl, alkenyl groups such as allyl and oleyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, and benzyl groups.

Examples of halogen-containing resins stabilized by the stabilizer of the present invention include vinyl halide homopolymers such as vinyl chloride resin, vinyl bromide resin, and vinylidene chloride resin, as well as vinyl halides, vinyl acetate, vinyl propionate, and butyric acid. Mention may be made of copolymers such as those formed by polymerization with one or more comonomers such as vinyl, vinylidene chloride, styrene, ethylene, propylene, methyl methacrylate, dialkyl fumarate, or malates and the like. can.

It is also applicable to mixtures of halogen-containing resins and impact-improving resins such as acrylonitrile-butadiene-styrene resins, methyl methacrylate-butadiene-styrene resins, vinyl acetate-ethylene copolymer resins, or chlorinated polyethylene resins.

The amount of the organic tin stabilizer having a functional group of the present invention added is 0.1 to 10 parts by weight per 100 parts by weight of the halogen-containing resin;
Usually 0.1 to 5 parts by weight is sufficient.

The halogen-containing resin stabilized composition of the present invention may also contain plasticizers, other stabilizers such as alkyltin compounds, metallic soaps, antioxidants, ultraviolet absorbers, lubricants, fillers, pigments, dyes, and other additives. An agent may be included if necessary.

When the organotin stabilizer having a functional group of the present invention is added to a halogen-containing resin, the following characteristics can be observed compared to conventionally known dialkyltin stabilizers.

That is, the thermal stability was improved for 5 to 10 minutes, making high temperature processing advantageous.

Secondly, the compatibility between the halogen-containing resin and the stabilizer has further improved, resulting in faster gelation and better cohesive processability, as well as improved lamination properties.

Thirdly, dialkyltin mercapto compounds generate mercaptan and irritating odors that make the work environment worse, but such unpleasant odors can be significantly reduced.

Next, production examples and examples are illustrated, and in each example, % is % by weight,
Parts represent parts by weight.

Production Example l Bis(ethoxycarbonylmethyl)tin dibromide (melting point 139'C) 45.
3,9. Isooctylthioglycolate 40,9,!
i' and benzene 1007! and ammonia water (
12.2 g of 28% aqueous solution) was added dropwise, and the reaction was carried out at 25 to 30°C for 30 minutes.

After the reaction, the mixture was separated and the organic layer was concentrated using an evaporator to obtain a quantitative amount of cis(ethoxycarbonylmethyl)tinbis(in-octylthioglycolate).

Tin content Actual value: 16.9% (Theoretical value: 17.0%)
Sulfur content Actual value 9.2% (Theoretical value 9.2%
) Production example 2 Potassium butyl male was added to a three-way flask equipped with a stirrer.
1-42, 1,! Charge i+ and acetone 400-.

A solution of 45.3 g of bis(ethoxycarbonylmethyl)tin dibromide dissolved in 50% of acetone was added dropwise to this while stirring.

After heating under reflux for 3 hours, it is filtered.

When the P solution is concentrated using an evaporator, bis(ethoxycarbonylmethyl)tin bis(butyl maleate) is obtained quantitatively.

Tin content Actual value: 18.6% (Theoretical value: 18.7%)
Example 1 100 parts of polyvinyl chloride (average degree of polymerization 800) and each stabilizer listed in Table 1 below were added so that the tin content was equal, and the mixture was heated to 170°C.
The mixture was mixed for 0.5 minutes to form a sheet with a thickness of 0.5 mm.

This sheet was placed in an oven maintained at 190°C and a thermal stability test was conducted.

The results are shown in Table 4.

As can be seen from Table 1, when the stabilizer of the present invention is used, the decomposition time is 5 to 10 minutes longer than when using the dibutyltin stabilizer.

Note that /168 and 10 had a mercaptan odor during processing, but /161, 3, 5, and 7 had almost no mercaptan odor.

Example 2 100 parts of polyvinyl chloride (average degree of polymerization 800), 2 parts of the following stabilizer, and 0.2 parts of lubricant WaxOP (manufactured by Hoechst) were mixed for 4 minutes with a mixer, and gelled with a Brabender Plastograph trowel. The time was measured.

The results are shown in Table 2.

Conditions for Brabender Plastograph Model Brabender Plastograph PL-3000-150 (manufactured by Haake, RHEOMIX 500) Jacket internal temperature 160°C Jacket volume 50m Sample weight 6 (10-ter rotation speed 4 Or, p, m Example 3 100 parts of polyvinyl chloride (average degree of polymerization: 800) and 2 parts of the following stabilizer were kneaded for 3 minutes using a mixing roll heated to 170°C to prepare a 0.5mmmm-t.

Six sheets of this were stacked and pressed at 170° C. and the same pressure for 15 minutes.

JIS by liquid paraffin immersion for each laminate
A K-6745 lamination test was conducted, and the quality of the lamination was determined by the gaps visible to the naked eye in the cross section of the test piece.

(Tested stabilizers) A: Bis(methoxycarbonylmethyl)tin bis(ethyl maleate) B: Bis(methoxycarbonylmethyl)tin maleate C Nidibutyltin bis(ethyl maleate) (Comparative example) D Nidibutyltin maleate (Comparative example) (Lamination Performance test results) The results were excellent in the following order:

A>B>C>D

Claims (1)

[Claims] 1. The halogen-containing resin has the general formula %) [wherein R is an alkyl group having 1 to 18 carbon atoms, and Y is a group -8(CH2)nCOOR'-SR'--OOCR'
or -00CCH=CHCOOR'(R' is 1 carbon number
an alkyl group, an alkenyl group, a cycloalkyl group, a benzyl group having ~18 groups, n is an integer of 1 to 4), Z is a group -
8-, -8m-. S (CH2) n COO or -00CCH=CHC
A halogen-containing resin stabilizing composition containing one or more organic tin compounds having a functional group represented by OO (m and n are integers of 1 to 4)