JPH0123502B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to mixtures of organotin compounds and chlorinated polymer and foam plastic materials containing them. It is disclosed in German Patent Publication No. 2003-11111 that a composition comprising an organotin mercaptide and an organotin compound selected from the group consisting of organotin, organotin carboxylate, organotin alcoholate and organotin oxide has a heat stabilizer effect. No. 1926949.
This publication specifically discloses a composition comprising an organotin thioglycolic acid ester and the organotin compound. Since organotin mercaptites are known to reduce the impact strength of hard polymers, a highly effective stabilizer that can be used in small amounts is strongly desired. Organotin compounds are also used as activators for the production of plastic foam products. These products are generally manufactured by methods known in the art, such as by blending the plastic material with a suitable blowing agent and injection molding using a molding temperature above the decomposition temperature of the blowing agent. However, the blowing agent cannot be used alone because the decomposition temperature of the blowing agent is often too high compared to the molding temperature. For this purpose, activators are often used which accelerate the decomposition of the blowing agent and/or reduce its decomposition temperature. DE 24 44 991 discloses activator systems consisting of organotin oxides, organotin alcoholates or mixtures thereof. The inventors have discovered that compositions consisting of organotin mercaptopropionic esters and organotin carboxylates impart surprisingly good light and thermal stability to chlorinated polymers, as well as for the production of foamed plastics. It was found to be an excellent activator. Therefore, the present invention provides organotin mercaptopropionate represented by the following formula: (R ¹ ) ₂ -Sn(-S-CH ₂ CH ₂ -COOR ⁵ ) ₂ () and the following formula or: (R ¹ - ) ₂ Sn(-OOC-R ⁶ ) ₂ () or (In the above formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, R ⁵ represents an alkyl group having 8 to 14 carbon atoms, and R ⁶ represents an alkyl group having 10 to 22 carbon atoms. ) for a polymer containing an organotin carboxylate represented by the formula in a weight ratio of 9:1 to 1:9 of an organotin mercaptopropionate represented by the formula: an organotin carboxylate represented by the formula or Stabilizer compositions and activator compositions for foamed plastics are provided. as C1 -C12 alkyl group
R ¹ is, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-amyl group, isoamyl group, n-hexyl group, n-heptyl group, n-octyl group , n-dodecyl group. Preferably R ¹ is a methyl group, n
-butyl group, n-amyl group, n-hexyl group or n-octyl group. Most preferably R ¹
is a methyl group, n-butyl group or n-octyl group. as C8 -C14 alkyl group
R ⁵ is, for example, a 2-ethylhexyl group, a decyl group,
These are dodecyl group and isotridecyl group. R ⁵ is preferably 2-ethylhexyl, dodecyl and isotridecyl, especially 2-ethylhexyl and isotridecyl. as C10 -C22 alkyl group
R ⁶ is, for example, a decyl group, a dodecyl group, an isotridecyl group, a tetradecyl group, an isooctadecyl group, a nonadecyl group, or a docosyl group. R ⁶ is preferably a 16-methylheptadecyl group, an isononyl group or an n-undecyl group. Examples of compounds of the formula are: dibutyltin bis(isotridecyl-β-mercaptopropionate) dibutyltin bis(2-ethylhexyl-β-
Mercaptopropionate) A preferred compound of the formula is dibutyltin bis(2-ethylhexyl-β-mercaptopropionate). Examples of compounds of the formula are: dibutyltin dilaurate dibutyltin diisooctadecylate. A preferred compound of the formula is dibutyltin diisooctadecylate. A compound of the formula is, for example, bis(dibutyl isodecanoyltin) oxide. The chlorinated polymer to which the stabilizer composition of the invention is added may be a homopolymer, such as polyvinyl chloride, polyvinylidene chloride, and the like. Suitable polymers are emulsions, suspensions and bulk polyvinyl chloride. The polymer may be a copolymer obtained by copolymerizing vinyl chloride or vinylidene chloride with other ethylenically unsaturated monomers. Ethylenically unsaturated monomers are compounds having a polymerizable carbon-carbon double bond (-C=C-); acrylates such as acrylic acid, ethyl acrylate, acrylonitrile; vinyl monomers such as styrene, vinyl acetate; maleic acid derivatives such as maleic acid. A group of compounds consisting of acids, maleates or esters, maleic anhydrides, and the like. The compositions of the invention can also be used as activators for foaming plastic materials. These plastic materials can be chlorinated polymers such as those mentioned above, but also polyesters, polylactones, polyamides, polyethers, polycarbonates and, preferably, polyols and the like. It is particularly preferred to use the compositions of the invention in polyvinyl chloride-based polymers, especially polyvinyl chloride (ie both plasticized PVC and rigid PVC). Rigid PVC stabilized with the compositions of the invention are particularly suitable for outdoor use. Organotin alcoholates as activators are known from DE 24 44 991 A1. Organotin alcoholates and organotin carboxylates as light and heat stabilizers for halogenated polymers are disclosed in the aforementioned German Patent Application No. 1926949 together with organotin mercaptocarboxylates. Organotin mercaptocarboxylates are also known from US Pat. No. 3,642,677. Organotin oxides are obtained by hydrolysis of the corresponding organotin halides. Organotin alcoholates are also obtained from the corresponding organotin halides and sodium alcoholates or from organotin oxides and alcohols. Organotin carboxylate is
It can be obtained by a simple reaction from the corresponding alkali salt of the acid and a water-soluble tin salt. In each of the above production methods, a particularly simple method is to simultaneously react reactants such as alcohol, carboxylic acid, mercaptan and tin. The amount of organotin compound in the substrate depends on economic and technical considerations. It is usually added in an amount of 0.1 to 0.3% by weight, especially 0.3 to 2% by weight, based on the polymer. The weight ratio of organotin compound: or is 9:
1 to 1:9, preferably 9:1 to 6:4
It is. If desired, customary additives, in particular antioxidants, light stabilizers or mixtures thereof, can also be added to the stabilized polymer compositions of the invention in an amount of 0.1 to 5% by weight, preferably 0.5 to 3% by weight.
Examples of such additives are: Antioxidants, such as 2,6-dialkylphenols, such as 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-4- Methylphenol, 2-tert-butyl-4,6-dimethylphenol, β-(3,5-di-tert-butyl-4-) of pentaerythritol or stearyl alcohol
hydroxyphenyl)-propionate esters (IRGANOX 1010 or IRGANOX 1076), and other additives such as bisphenol A, UV absorbers and light stabilizers (e.g. 2-(2'-hydroxyphenyl)-
Benztriazole, 2,4-bis(2'-hydroxyphenyl)-6-s-triazine, 2-hydroxybenzophenone, 1,3-bis-(2'-hydroxybenzoyl)-benzene, unsubstituted or substituted esters of benzoic acid, acrylates), and also nickel compounds, sterically hindered amines, oxalic diamides or other additives (e.g. plasticizers,
Lubricant, emulsifier, filler, carbon black, asbestos, kaolin, talc, glass fiber, pigment,
fluorescent brighteners, flame retardants, antistatic agents). The organotin compound compositions of the present invention can be blended with polymers in a known manner by known mixing means. For this purpose, blowing agents for foamed plastic materials can be added together with organotin activators, or the activators can be blended into plastic materials that already contain blowing agents. In order to obtain as homogeneous a composition as possible, it is advantageous to blend the components in powder form; however, it is also possible to use granular plastics, in which case a suitable blowing agent and/or organotin activator may be used. Additional binders can also be used to obtain good accessibility. The compositions of the present invention are surprisingly effective heat and light stabilizers. This excellent light protection makes the stabilized polymers particularly suitable for outdoor use. Furthermore, the compositions of the invention are surprisingly suitable active agents for the production of foamed plastics. The invention will be explained in more detail by the following examples. In the examples, parts and percentages are by weight unless otherwise specified. Example 1 Dibutyltin bis(2-ethylhexyl-β-
Mercaptopropionate) 25.0g (0.1mol) of dibutyltin oxide in 2-
43.6g of ethylhexyl thiopropionate,
The reaction was carried out at 110° C. under reduced pressure using a water jet pump until the water produced in the reaction was completely removed. Analytical value of reaction product: Sn 17.1%, n ^D ₂₀ = 1.5015 Example 2 (simultaneous reaction) (C-H ₉ -) ₂ Sn (-S-CH ₂ CH ₂ -COO-i
-C ₁₃ H ₂₇ ) ₂ (29.6%) (C ₄ H ₉ -) ₂ Sn (-OOC-i-C ₁₇ H ₃₅ ) ₂
(40.4%) and (C ₄ H ₉ -) ₂ Sn (-O-i-C ₁₃ H ₂₇ ) ₂ (30.0%) 62.7 g of dibutyltin oxide was added to boiling toluene.
In 350 ml, 36.0 g (0.18 mol) isotridecanol, 56.1 g (0.18 mol) isostearic acid and 41.6 g isotridecyl thiopropionate.
(0.14 mol) was reacted while removing the water produced in the reaction. Then remove toluene and colorless liquid 195
I got g. Analysis value: Sn 14.15%, n ^D ₂₀ =1.4831 The weight ratio of the compound was 3:4. Example 3 (Simultaneous reaction) (C ₄ H ₉ -) ₂ Sn (-S-CH ₂ CH ₂ -COO-i-
C ₁₃ H ₂₇ ) ₂ (52.0%) (C ₄ H ₉ -) ₂ Sn (-OOC-i-C ₁₇ H ₃₅ ) ₂
(27.6%) and (C ₄ H ₉ -) ₂ Sn (-O-i-C ₁₃ H ₂₇ ) ₂ (20.4%) 32.15 g (0.129 mol) of dibutyltin oxide in 150 ml of boiling toluene So, isotridecanol
12.91g (0.065mol), isostearic acid 20.08g
(0.065 mol) and 37.18 g (0.129 mol) of isotridecylthiopropionate while removing water produced by the reaction. The toluene was then removed to obtain a colorless liquid. Analysis value: n ^D ₂₀ = 1.488 Example 4 where the weight ratio with the compound was 1.9:1 V (C ₄ H ₉ -) ₂ Sn (OOC-C ₁₁ H ₂₃ )-O-Sn-(
C ₄ H ₉ ) ₂ (OOC―C ₁₁ H ₂₃ ) (70%) (C ₄ H ₉ ―) ₂ Sn(―S―CH ₂ CH ₂ ―COO―i―
Composition consisting of C ₈ H ₁₇ ) ₂ (30%) 39.6 g (0.159 mol) of dibutyltin oxide was reacted with 31.8 g (0.159 mol) of lauric acid at 110° C. while removing water produced by the reaction. The obtained liquid reaction product was mixed with 30 g of dibutyltin bis(2-ethylhexyl-β-mercaptopropionate) obtained in Example 1. Analysis value: Sn 24.5%, n ^D ₂₀ =1.4928 The weight ratio with the compound was 1:2.3. Example 5 (Simultaneous reaction) (C ₄ H ₉ -) ₂ Sn (-S-CH ₂ CH ₂ -COO-i-
C ₁₃ H ₂₇ ) ₂ (28.8%) (C ₄ H ₉ -) ₂ Sn (-OOC-i-C ₁₇ H ₃₅ ) ₂
(38.6%) (C ₄ H ₉ -) ₂ Sn (-O-i-C ₁₃ H ₂₇ ) ₂ (28.6%) + Irganox 1076 (4%) 32.7 g (0.13 mol) of dibutyltin oxide Isotridecanol in 150ml of boiling toluene
18.8g (0.09mol), isostearic acid 29.2g
(0.09 mol) and 21.7 g (0.07 mol) of isotridecyl thiopropionate while removing water produced in the reaction. After removing toluene, 4.0 g of Irganox 1076 was dissolved in the residue. After evaporation, a liquid with the following analytical values was obtained: Sn: 15.0%, d ₂₀ : 1.021, n ^D ₂₀ : 1.4817 The weight ratio of compound to compound was 3:4. Example 6 (C ₄ H ₉ -) ₂ Sn (-S-CH ₂ CH ₂ -COO-i-
C ₁₃ H ₂₇ ) ₂ (28.8%) (C ₄ H ₉ -) ₂ Sn (-OOC-i-C ₁₇ H ₃₅ ) ₂
(53.9%) (C ₄ H ₉ -) ₂ Sn (-O-i-C ₁₃ H ₂₇ ) ₂ (13.3%) + Irganox 1076 (4%) mixture component 1 (dibutyltin alcoholate-carboxylate) Dibutyl In 150 ml of boiling toluene, 21.0 g (0.08 mol) of tin oxide was dissolved in 39.3 g of isostearic acid.
g (0.13 mol) and isotridecanol 8.4 g
(0.04 mol) was reacted with water produced in the reaction while removing it. The toluene was then removed by distillation. Component 2 (dibutyltin isotridecyl-bis-thiopropionate) 8.9g (0.036 mol) of dibutyltin oxide to 110%
Isotridecyl thiopropionate 20.46 °C
g (0.072 mol) was reacted with water produced in the reaction while distilling and removing it. Take 67.2g of component 1 and 28.8g of component 2, and add 50
C. and then 4.0 g of Irganox 1076 was dissolved into this mixture. After evaporation, a liquid with the following analytical values was obtained. Sn: 14.2%, d (20°): 1.033, n ^D ₂₀ : 1.4861 The mixing ratio with the compound was 1:1.9. Example 7

[Table] 23.8 g (0.096 mol) of dibutyltin oxide in 110
The mixture was reacted with 10.5 g (0.049 mol) of nonylphenol and 44.4 g (0.143 mol) of isostearic acid at °C while removing water produced in the reaction. The obtained liquid reaction product was dibutyltin bis(2-ethylhexyl-β-mercaptopropionate).
19.0 g and Irganox 1076 (4.0 g). Analysis value: Sn: 14.6%, n ^D ₂₀ =1.4862 The weight ratio with the compound was 1:3.2. Usage test example 8 Mill aging test PVC [Vestlit HIS (Vestlit HIS)
6882] 100 parts, titanium dioxide 4 parts and Example 4
A dry blend consisting of 2.5 parts of the stabilizer composition was run on a mill aging test at 200°C and samples were taken every 3 minutes to measure the yellowness index (YI).

[Table] Example 9 Weathering test PVC (Bestrit H.S. 6822)
100 parts, titanium dioxide, 4 parts, and 2.5 parts of the stabilizer composition described below were mixed in a high speed mixer. The mixture was treated in a laboratory roll mill for 5 minutes at 180°C.
It was rolled into a sheet, and a transparent sheet with a thickness of 0.5 mm was pressed from this sheet using a step press. Accelerated weathering tests were conducted using this sheet (Xenotest 1200 lamp, original
Original Hanau Quarzlampen GmbH, Hanau, West Germany. The exposure cycle was 29 minutes of xenon-arc lamp irradiation and 1 minute of exposure to artificial rain. The above exposures were alternated. In the table below, time refers to the total exposure time in hours. The test value indicates the yellowing process using the yellowness index.

[Table] Example 10 PVC (Bestrit H.S. 6882)
The weathering test of Example 9 was repeated using a dry blend consisting of 100 parts titanium dioxide, 4 parts titanium dioxide, and 2.5 parts of the stabilizer composition of Example 4, except that the exposure was done with a Xenotest 150 lamp. The results are shown in the table below.

Table: Even after 1200 hours of exposure, the sheet showed no discoloration. Example 11: Dynamic heating test 100 parts of PVC suspension (K value approximately 65), 6.0 parts of calcium carbonate, processing aid (acrylic polymer, K-
120N), 3.0 parts of ABS terpolymer, 2.0 parts of titanium oxide, 0.8 parts of paraffin wax, and 2.0 parts of one of the following stabilizer mixtures are uniformly mixed.

[Table] Mix this dry blend in a two-roll mill at 190°C. Samples with a thickness of 0.3 mm are cut from the film formed on one side of the roll every 5 minutes. The degree of coloration of the sample was determined by measuring the optical reflectance using a tristimulus colorimeter and determining the plastic yellowness index (Y.
I.) Measured according to ASTM D 1925-70. The results are shown in the table below.

[Table] PVC without stabilizer became significantly colored and decomposed almost simultaneously at 190°C. Example 12: A. Dynamic heating test 100 parts of PVC suspension (K value approximately 65), 6.0 parts of calcium carbonate, processing aid (acrylic polymer, K-
120N), 3.0 parts of ABS terpolymer, 2.0 parts of titanium oxide, 0.8 parts of paraffin wax, and 2.0 parts of one of the following stabilizer mixtures are uniformly mixed. Stabilizer mixture number 12.1: (n—C ₄ H ₉ ) ₂ Sn (—SCH ₂ CH ₂ COO—iso—
C ₁₃ H ₂₇ ) ₂ 90 copies (n-C ₄ H ₉ ) ₂ Sn (-OCOC ₁₁ H ₂₃ )-O-Sn(n-
C ₄ H ₉ ) ₂ (—OCOC ₁₁ H ₂₃ ) 10 parts Stabilizer mixture number 12.2: (n—C ₄ H ₉ ) ₂ Sn (—SCH ₂ CH ₂ COO—iso—
C ₁₃ H ₂₇ ) ₂ 75 parts (n-C ₄ H ₉ ) ₂ Sn(-OCOC ₁₁ H ₂₃ )-O-Sn(n
—C ₄ H ₉ ) ₂ (—OCOC ₁₁ H ₂₃ ) 25 parts Stabilizer mixture number 12.3: (n—C ₄ H ₉ ) ₂ Sn (SCH ₂ CH ₂ COO—iso—
C ₁₃ H ₂₇ ) ₂ 50 copies (n-C ₄ H ₉ ) ₂ Sn(-OCOC ₁₁ H ₂₃ )-O-Sn(n
-C ₄ H ₉ ) ₂ (-OCOC ₁₁ H ₂₃ ) 50 parts Mix this dry blend in a two-roll mill at 190°C. Cut the film formed on one side of the roll into 0.3 mm thick samples every 5 minutes. The degree of coloration of the samples was determined by measuring optical reflectance using a tristimulus colorimeter according to Yellowness Index (YI) of plastics ASTM D 1925-70. The results are shown in the table below.

[Table] PVC without stabilizer became significantly colored and decomposed almost simultaneously at 190°C. B. Active ingredients of the blowing agent for producing foamed vinyl chloride polymers: 10 parts of dioctyl phthalate and 1 part of azodicarboxamide (common blowing agents for producing foamed vinyl chloride polymers) plus stabilizer mixture No. 12.1 as described in A above. Mix 2 parts of 12.2 or 12.3. A portion of the portion defined above is heated in a flask and maintained at a constant temperature. The flask was connected to a gas bottle and the amount of gas evolved was read at specific time intervals: 1.0, 2.5, 5.0 and 10 minutes. Tests were conducted separately between 160° and 220°C, the temperature range in which the evolved gas is effectively utilized for foam generation. The amount of gas generated is expressed in ml. The results are shown in the table below.

[Table] Example 13: Dynamic heating test 100 parts of PVC suspension (K value approximately 65), 0.2 parts of paraffin wax and (n-C ₄ H ₉ ) ₂ Sn (-
SCH ₂ CH ₂ COO―iso―C ₈ H ₁₇ ) ₂ 1.0 part, [(n―
2.0 parts of a stabilizer mixture consisting of 0.5 parts of C ₄ H ₉ ) ₂ Sn (OCO—C ₁₁ H ₂₃ )] ₂ O are mixed homogeneously (stabilizer mixture no. 13.1). This dry blend is mixed in a two-roll mill at 200°C. The film formed on one side of the roll is cut into 0.3 mm thick samples every 3 minutes. The degree of coloration of the samples was determined by measuring optical reflectance using a tristimulus colorimeter according to Plastic Yellowness Index (YI) ASTM D 1925-70. The results are shown in the table below.

[Table] PVC without stabilizer became significantly colored and decomposed almost simultaneously at 200°C. Example 14: Static heating test a 15.32 g of dioctyltin oxide was mixed with 2-ethylhexyl-β-mercaptopropionate.
Mix with 18.53g. While stirring, heat this mixture in vacuo (20 mbar) at 100 °C for 25 minutes. Dioctyltin-bis-(2-ethylhexyl-β-mercaptopropionate) 32.7
g is obtained as a pale yellow liquid. b 45.96 g of dioctyltin oxide and 6.06 g of 2-ethylhexanecarboxylic acid and lauric acid
Mix with 16.83g. While stirring, heat this mixture in vacuo (20 mbar) at 100 °C for 25 minutes. Basic dioctyltin carboxylate represented by the following formula: [(C ₈ H ₁₇ ) ₂ Sn (OOCR)] ₂ O (wherein OOCR represents a mixture of 2-ethylhexanoyloxy and lauroyloxy groups) 67.3 g are obtained as a colorless oily liquid. The products obtained according to a) and b) are mixed and filtered. The mixture is a colorless liquid with n ²⁰ _D = 1.4885 and density d ₂₀ = 1.078. Tin content: 19.5 (calculated: 19.9); Sulfur content: 2.6 (calculated: 2.7). The mixture has the following formula: 32.2% by weight of a compound represented by and the following formula: [( _C8H17 ) _2Sn (OOCR)] _2O (wherein -OOCR represents a mixture of 2 _- ethylhexanoyloxy and lauroyloxy groups.) It consists of 67.3% by weight of the compound represented by This mixture is subjected to a static heating test as follows. 100 parts of PVC suspension (K value 60) are uniformly mixed with 1 part of lubricant (wax e) and 2.5 parts of the above mixture. This dry blend was kneaded in a two-roll mill at 190°C for 5 minutes to obtain a PVC sheet with a thickness of 0.3 mm. Cut samples of this sheet and heat them in an oven to 190°C. The thermal aging of the samples is determined every 5 minutes by measuring the yellowness index (YI) according to the standard method ASTM D 1925-70. The results are shown below.

【table】

Claims (1)

[Claims] Organotin mercaptopropionate represented by the following formula: (R ¹ ) ₂ -Sn(-S-CH ₂ CH ₂ -COOR ⁵ ) ₂ () and the following formula or: (R ¹ ) ― ₂ Sn(−OOC—R ⁶ ) ₂ () or (In the above formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, R ⁵ represents an alkyl group having 8 to 14 carbon atoms, and R ⁶ represents an alkyl group having 10 to 22 carbon atoms. ) for a polymer containing an organotin carboxylate represented by the formula in a weight ratio of 9:1 to 1:9 of an organotin mercaptopropionate represented by the formula: an organotin carboxylate represented by the formula or Stabilizer composition. 2. The stabilizer composition for polymers according to claim 1, wherein R ¹ in the above formula represents an n-butyl group. 3. The stabilizer composition for polymers according to claim 1, wherein R ⁵ represents a 2-ethyl-hexyl group. 4. The stabilizer composition for polymers according to claim 1, wherein R ⁶ in the above formula represents an n-undecyl group. 5. The stabilizer composition for polymers according to claim 1, wherein the polymer to be stabilized is a chlorinated polymer. 6. The stabilizer composition for polymers according to claim 5, wherein the chlorinated polymer is hard polyvinyl chloride. 7 Organotin mercaptopropionate represented by the following formula: (R ¹ ) ₂ —Sn(—S—CH ₂ CH ₂ —COOR ⁵ ) ₂ ( ) and the following formula or: (R ¹ —) ₂ Sn(—OOC ―R ⁶ ) ₂ () or (In the above formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, R ⁵ represents an alkyl group having 8 to 14 carbon atoms, and R ⁶ represents an alkyl group having 10 to 22 carbon atoms. ) A foamed plastic containing an organotin carboxylate represented by the following formula in a weight ratio of 9:1 to 1:9: organotin mercaptopropionate represented by the formula: organotin carboxylate represented by the formula or activator composition for use. 8. The activator composition for foamed plastics according to claim 7, wherein R ¹ represents an n-butyl group in the above formula. 9. The activator composition for foamed plastics according to claim 7, wherein R ⁵ in the above formula represents a 2-ethyl-hexyl group. 10. The activator composition for foamed plastics according to claim 7, wherein R ⁶ in the above formula represents an n-undecyl group.