KR840001239B1 - Organo stannic stabilizing compounds for vinyl halide resins - Google Patents

Abstract

Organo stannic stabilizers for vinyl halide resins, esp. polyvinyl chloride, are prepd. by reacting organo stannic trihalogen compd. R1'SnHal3 with mercatoalkyl ester HS(CH2)n R1'Sn[S(CH2) nOC(=0)R6 3. R1' is R1C(=0)C(-R2)=c(-R3)(-R4); R2, R3, and R4 are H or C1-3 alkyl; R1 is alkyl, hydroxy, or oxygen-contg. hydrocarbon; R6 is C1-18 alkyl; and n is 2, 3, or 4.

Description

Manufacturing method of organic tin stabilizer for vinyl halide resin

The present invention relates to a process for producing a novel organotin stabilizer for vinyl halide resins.

이때 R₁′은 탄소-탄소이중결합에 인접된 카보닐기를 함유하는 올레핀 화합물의 기이다. 그러한 올레핀화합물은 다음과 같은 화학식을 가지고 있다.The new organotin stabilizer of the present invention has the following formula:

R ₁ ′ is a group of the olefin compound containing a carbonyl group adjacent to a carbon-carbon double bond. Such olefin compounds have the following formula.

In this case, R ₂ , R ₃ , R ₄ is hydrogen or an alkyl hydrocarbon group having 1 to 3 carbon atoms, and R ₁ is a hydrocarbon group containing an alkyl group, a hydroxyl group or oxygen.

은 머켑토 알킬에스테르의 기이며, 이때 머켑토그룹은 에스테르의 알콜기내에 함유되어 있고, R₆은 1개 내지 18개의 탄소원자를 갖는 알킬이다. 그것은 지방족의 1 염기산 또는 2 염기산에 속할 수 있다. 그러나 바람직한 에스테르는 지방산, 특히 카프릴산, 페라곤산, 카프린산, 언데칸산, 라우린산, 미리스틴산, 팔미틴산, 스테아린산 및 이소스테아린산 또는 이들산의 혼합물로부터 유도된다.These olefin compounds contain methyl, ethyl or hexyl acrylate, acrylic acid, vinyl methyl ketone and methyl crotonate. Base

Is a group of the mucto alkyl ester, wherein the mucto group is contained in the alcohol group of the ester, and R ₆ is alkyl having 1 to 18 carbon atoms. It may belong to aliphatic monobasic or dibasic acids. However, preferred esters are derived from fatty acids, in particular caprylic acid, peragonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid and isostearic acid or mixtures of these acids.

은 유기주석트리할로겐화합물 R₁SnHal₃과 머켑토 알킬에스테르

즉 종전의 방법에서 기술된 특정생성물의 경우에 있어서와 같이 머켑토기가 에스테르의 알킬기에 존재하며 산기에는 존재하지 않는 에스테르의 반응에 의하여 얻어진다. -SH 기의 위치에 있어서 이러한 차이 때문에 새로운 유기주석 에스테르의 찬성은 현저한 효과를 가져온다는 것을 발견한 것은 놀랄만하다. 또한 상기 물질의 제조 및 정제가 용이하다는 장점을 가지고 있다.“N” is 2, 3, or 4 and one of CH ₂ may be replaced with a hydroxyl group. These new organic stone stabilizers

Silver Organotin Trihalogen Compound R ₁ SnHal ₃

That is, as in the case of the specific product described in the previous method, the mercotto group is obtained by the reaction of an ester which exists in the alkyl group of the ester and which does not exist in the acid group. It is surprising to find that due to this difference in the position of the -SH group, the pros of the new organotin esters have a significant effect. It also has the advantage that the preparation and purification of the material is easy.

The trihalogenated stannic trihalides themselves are prepared according to the method described in French Patent No. 2,285,392 or in the French patent application filed by Societe Nacional Elf Aquiquene Company on the same date as the present invention. Tin compounds can thus be obtained by reacting a sufficient amount of olefin compound of formula (1) with no solvent in the presence of hydrogen acid in the stomach.

This new organotin compound has excellent properties for the stabilization of vinyl halide resins, in particular polyvinyl chloride. This stabilizer makes it possible to suppress discoloration of the vinyl halide resin during heating without disturbing viscosity control.

This new organotin compound can be used alone or in combination with other tin stabilizers known from previous methods. In particular between 5% -95% of monoalkyl and 95% -5% of dialkyltin such as, for example, Cl-n-butyltinbis (isooctylmercetoacetate) Bu ₂ Sn (CH ₂ CO ₂ iCH ₁₇ ) ₂ Excellent results are obtained by using the ratio of.

Halogen-containing resins to which the present invention is to be applied include a homer polymer such as polyvinyl chloride, polyvinylidene chloride, polychlorotrifluoroethylene, polytetrafluoroethylene, polychloroether, polydichlorostyrene, and the like. And copolymers such as polyvinyl chloride modified with acrylonitrile butadiene styrene, ethylene vinyl acetate, etc. by methirene or propylene. This new stabilizer can be blended into the resin after polymerization or prior to drying of the polymer or upon use of the polymer. Their proportion can vary within a wide range, in particular up to 0.1% -5%, preferably 0.5-2%, of the resin weight.

Example 1

의 제조(3 - 메톡시카복실 - 에틸) - 트리스(2 - 팔미토일옥시 - 에틸티오) 주석의 제조][stabilizator

Preparation of (3-methoxymethoxy-ethyl) -tris (2-palmitoyloxy-ethylthio) tin]

A 500 ml round bottom flask with a stirrer and thermometer is placed on a heating bath.

7.8 g (0.025 mol) of Cl ₃ SnCH ₂ CH ₂ COOCH _3, 23.7 g (0.075 mol) of mercitoethyl palmitate and 300 ml of dried hexane are placed in a flask. Heat until the materials are completely dissolved and then leave the temperature until 40 ° C. 7.6 g (0.075 mol) of triethanalamine is then added dropwise and held at 40 ° C. for 3 hours. Triethylamine hydrogen chloride precipitate is filtered off. 18.5 g of a white solid was obtained in the cooled filtrate. The characteristics analyzed are as follows.

CH ₃ OCOCH ₂ CH ₂ Sn (SCH ₂ CH ₂ OCOC ₁₅ H ₃₁ ) ₃

Assay: C ₅₈ H ₁₁₂ O ₈ S ₃ Sn: 1151

Calculation: C: 60.47%, H: 9.7%, S: 8.34%, Cl: 0

Found: C: 60.89%, H: 9.91%, S: 8.32%, Cl: 0

An additional amount (5.1 g) of the desired product was recovered from the mother liquor.

Example 2

[Preparation of (3-methoxycarbonylethyl) -tris- (2-myristooxyethylthio) tin]

21.8 g (0.07 mol) of Merchantoethyl Myristate and 450 ml of dry hexane were placed on a heating bath equipped with a stirrer, thermometer and dropping funnel (trichloro) (2-methoxycarbonylethyl) tin. Place in a 1 liter round bottom flask, heat until completely dissolved, and leave until temperature drops to 40 ° C. Then, 21.3 g (0.21 mol) of chlorethylamine dissolved in 50 ml of hexane was added dropwise. It is then heated at 40 ° C. for 3 hours. 29 g of butylamine hydrochloride (that is, 100% of the theoretical amount) of the formed tree is filtered out. The filtrate was cooled to 0 ° C. and filtered to give 63.2 g of a white crystalline solid. This product is characterized by the following formula:

CH ₃ OCOCH ₂ CH ₂ Sn (S (CH ₂ ) ₂ OCOC ₁₃ H ₂₇ ] ₃

Assay: C ₅₂ H ₁₀₀ O ₈ S ₃ Sn: 1067

Calculation: C: 58.48%, H: 9.35%, S: 9.00%

Found: C: 58.46%, H: 9.58%, S: 9.04%

Example 3

[Production of (3-methoxycarbonylethyl) -tris- (2-stearoethoxyethylthio) tin]

The working method in this example is the same as described in Example 2, in which 15.6 g (0.05 mol) of Cl ₃ SnCH ₂ CH ₂ CO ₂ CH ₃ and 51.6 g (0.15 mol) of mercito-ethylstearate are placed in a flask. . After the treatment, 47.5 g of a white solid having a melting point of 57 DEG C, that is, a yield of 77% was obtained. This product was found to be the desired product by spectroscopic analysis.

CH ₃ OCOCH ₂ CH ₂ Sn (SCH ₃ CH ₂ OCOC ₁₇ H ₃₅ ) ₃

Example 4

형 화합물의 안정효과(안정제 B)

Stabilization effect of the compound (stabilizer B)

In this example, a discoloration test by heating was performed on a sample of polyvinyl chloride stabilized with the compound prepared in Example 1. To this end, the following composition is mixed with a roller mixer at 185 degrees Celsius.

100 parts by weight of polyvinyl chloride, known under the trademark LACOVYL SO71S with a viscosity coefficient of K = 56.

-0.5 part of "E" wax forming a surface lubricant

0.5 parts of the stabilizer prepared in Example 1

Under these conditions, a resin having excellent color is obtained. Discoloration of the resin was observed, the onset of discoloration was 9-10 minutes, and the sample was brown for 14 minutes. This result is similar to that observed using the corresponding butyltin compound BuSn (SCH ₂ CH ₂ OCOC ₁₅ H ₃₁ ) ₃ .

Example 5

(안정제 B)형의 안정제를 디알킬주석(안정제 C)과 함께 조합시킨 혼합물의 안정화효과, R₁′=C₁₃,C₁₅,C₁₇인 상기 형태의 안정제를 디-n-부틸주석-비스(이소옥틸머켑토아세테이트)와 함께 사용하였다.

Stabilizing effect of a mixture of a stabilizer of type (stabilizer B) together with a dialkyltin (stabilizer C), a stabilizer of the above form wherein R ₁ ′ = C ₁₃ , C ₁₅ , C ₁₇ is di-n-butyltin-bis (Isooctyl mercetoacetate) was used.

The mixture is composed as follows.

-100 parts by weight of polyvinyl chloride

-Stabilizer B 0.1 part

Stabilizer C 0.2 parts

0.5 parts of “E” wax

The results as an essential function of group R are listed in Table I below and are compared with a mixture comprising only stabilizer C.

TABLE I

From the table, it can be concluded that Formulation 2-4 has a synergistic effect in terms of initial color and long-term stability compared to Formulation 1.

Example 6

This example shows the favorable effect of the formulation 2-4 of Example 5 on the viscosity of polyvinyl chloride. The measurement described is carried out using a Brabender device capable of recording the time-dependent change in the mixed rotational power of the resin at a given temperature.

The formulation is as follows.

100 parts by weight of polyvinyl chloride

CaCO ₃ 3 parts by weight

1 part by weight of TiO ₂

0.8 weight part of "E" wax

BuSn (SCH ₂ CO ₂ C ₈ H ₁₇ ) ₂ 0.75 parts by weight

CH ₃ OCO (CH ₂ ) ₂ Sn [S (CH ₂ ) ₂ OCOC ₁₅ H ₃₁ ] ₃ 0.72 parts by weight

Experiment at the rotational speed of the mixer rotor at 60 ℃ under 200 ℃. The resulting curve shows a standing period of about 16 minutes with a torque of 1.6 m.kg.

Claims (1)

As stabilizer compositions due to polyvinyl halides, in particular polyvinyl chloride,

Contains one or more compounds of wherein R ′ is one olefin group

Wherein R ₂ , R ₃ and R ₄ represent hydrogen or an alkyl hydrocarbon group containing 1 to 3 carbon atoms, R ₁ represents an alkali group, a hydroxyl group or a hydrocarbon group containing oxygen,

The group is a mercetoalkyl ester group, wherein the merceto group is contained in an alcohol group of the ester, R ₆ is an alkyl group containing 1 to 18 carbon atoms, n is 2, 3 or 4 and one of CH ₂ is a hydroxyl group These compounds which may be substituted are organotin trihalides R ₁ ′ SnHal ₃ by the

Process for producing an organotin stabilizer for vinyl halide resin, characterized in that the reaction with.