CN102675770A - Sn-Sb-Zn composite heat stabilizer for polyvinyl chloride (PVC) sheets and preparation method and application thereof - Google Patents
Sn-Sb-Zn composite heat stabilizer for polyvinyl chloride (PVC) sheets and preparation method and application thereof Download PDFInfo
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- CN102675770A CN102675770A CN2012101301149A CN201210130114A CN102675770A CN 102675770 A CN102675770 A CN 102675770A CN 2012101301149 A CN2012101301149 A CN 2012101301149A CN 201210130114 A CN201210130114 A CN 201210130114A CN 102675770 A CN102675770 A CN 102675770A
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Abstract
The invention discloses a Sn-Sb-Zn composite heat stabilizer for polyvinyl chloride (PVC) sheets. The Sn-Sb-Zn composite heat stabilizer comprises, by weight, 10-20 parts of thioglycolic acid methyl tin, 40-60 parts of thioglycolic acetic ester antimony and 5-15 parts of organic acid zinc salt. The invention further discloses the preparation method of the Sn-Sb-Zn composite heat stabilizer and application of the Sn-Sb-Zn composite heat stabilizer as a PVC stabilizer. The composite heat stabilizer is high in product quality, low in toxicity, environment-friendly, less in tin content in a formula and applicable to various PVC hard sheet materials, has good initial and long-term heat stability, and is high in product transparency.
Description
(1) technical field
The present invention relates to plastic processing technology, more particularly relate to a kind of PVC sheet material with Sn-Sb-Zn composite thermal stabilizer and preparation method thereof.
(2) background technology
SE (PVC) is widely used for exhausted starting material, building materials and daily plastic goods with its cheap price with excellent performance.In recent years, China two stable figure place growing trends still occur to the aggregate demand of PVC.But because there is textural defect in the PVC molecular chain; Can deviate from hydrogenchloride when being heated to 110 ℃, the hydrogenchloride of emitting can quicken the decomposition of PVC again, so PVC when 160 ℃-200 ℃ of processing temperatures obvious degradation can take place; Cause the decline such as variable color and products machinery performance of product, influence work-ing life.For prevent that PVC from degrading in the course of processing, need to add thermo-stabilizer, thermo-stabilizer commonly used has lead salts, metallic soap class, rare earth class and organic tin etc.
In recent years, the PVC thermo-stabilizer develops towards low toxicity, efficient, free of contamination direction, and the organic tin thermo-stabilizer has many advantages, like good thermostability, the transparency and consistency etc., is that present purposes is the widest, one of thermo-stabilizer that effect is best.
But present methyl tin heat stabilizer is main with single methyl tin compound mostly, and shortcoming such as have that cost is high, self-lubricating property difference and initial coloring are not enough causes its competitive power in stablizer market not enough.
Related patent U.S. Patent No. is many both at home and abroad at present is main with synthetic organo-tin het stabilizer, about its compounded technology report seldom.Patent CN 1631963A proposes to form the Ca-Zn-Sn one package stabilizer with calcium stearate, Zinic stearas and organotin, but because calcium stearate and Zinic stearas fusing point are higher, is difficult to be dissolved in the organotin, therefore can only make solid-state stablizer.
(3) summary of the invention
To the problem that PVC methyl tin stabilizer in the prior art exists, PVC sheet material provided by the invention is used the Sn-Sb-Zn composite thermal stabilizer, and it exists with liquid form, and purpose is intended to solve following technical problem:
1, the tin content in the reduction methyl tin heat stabilizer reduces the consumption and the pollution thereof of rare metal tin;
2, further improve the initial stage and the long-term thermal stability of PVC sheet material products;
3, enlarge the range of application of PVC with stablizer;
4, reduce methyl tin heat stabilizer and PVC goods cost.
In order to reach the foregoing invention purpose, the technical scheme that the present invention adopts is:
A kind of PVC sheet material is used the Sn-Sb-Zn composite thermal stabilizer, it is characterized in that said PVC sheet material comprises the component of following weight part with the Sn-Sb-Zn composite thermal stabilizer:
10～20 parts in Thiovanic acid methyl tin
40～60 parts in mercaptoacetate antimony
5～15 parts of organic acid zinc salts
Described Thiovanic acid methyl tin is S; S '-two (Thiovanic acid) tin methide and S; S ' S " mixture of-three (Thiovanic acid) monomethyl tin; being under alkaline condition, is that 80: 20 the dimethyltin chloride and the mixture and the Thiovanic acid of monomethyl tin trichloride prepare with esterification process by mass ratio;
Said mercaptoacetate antimony is the mixture of any one or both above arbitrary proportions shown in formula III;
In the formula III, R
1Be the straight chain saturated alkyl of C2-C8, n=3 or 5;
Said organic acid zinc salt is a zinc oleate, any one in isocaprylic acid zinc or the p-tert-butyl benzoic acid zinc.
Further, PVC sheet material according to the invention is made up of the component of following weight part with the Sn-Sb-Zn composite thermal stabilizer:
10～20 parts in Thiovanic acid methyl tin
40～60 parts in mercaptoacetate antimony
5～15 parts of organic acid zinc salts.
Thiovanic acid methyl tin according to the invention can make by following method: under alkaline condition; By mass ratio be 80: 20 dimethyltin chlorides and monomethyl tin trichloride mixture, mix with mass ratio 1: 1～1.1: 3～4 with Thiovanic acid and water again; Under 60～80 ℃ of temperature; Using ammoniacal liquor to regulate the pH value is 7～8, reacts 2～5 hours after-filtration, and underpressure distillation obtains said Thiovanic acid methyl tin.This is to well known to a person skilled in the art the esterification preparation method.
Prepared Thiovanic acid methyl tin is suc as formula the S shown in the I, S '-two (Thiovanic acid) tin methide and suc as formula the S shown in the II, S ' S " mixture of-three (Thiovanic acid) monomethyl tin:
Mercaptoacetate antimony of the present invention is preferably any one in tri-thiol 2-ethyl hexyl ethanoate antimony, five isooctyl mercaptoacetate antimony, tri-thiol ETHYLE ACETATE antimony or the five ethyl thioglycolate antimony, most preferably tri-thiol 2-ethyl hexyl ethanoate antimony.
PVC sheet material according to the invention can prepare by following method with the Sn-Sb-Zn composite thermal stabilizer:, Thiovanic acid methyl tin and mercaptoacetate antimony are mixed control stirring velocity 80～150r/min according to the feed composition proportioning; Controlled temperature is at 65～120 ℃; Behind reaction 0.5～3h, drop into the organic acid zinc salt again and mix 1-2h, be cooled to room temperature then; Filter, getting filtrating and being said PVC sheet material and using the Sn-Sb-Zn composite thermal stabilizer.
PVC sheet material of the present invention is inferred the structure tin antimony compsn shown in the structural formula as follows with the Sn-Sb-Zn composite thermal stabilizer:
Wherein R is the straight chain saturated alkyl of C2-C8.
PVC sheet material of the present invention can be used the thermo-stabilizer as PVC with the Sn-Sb-Zn composite thermal stabilizer; Concrete, the method for said application is: the PVC sheet material that adds 0.8 part～1.2 mass parts in the SE of per 100 mass parts with the Sn-Sb-Zn composite thermal stabilizer as thermo-stabilizer.
The present invention beneficial effect be mainly reflected in:
1, the composite thermal stabilizer quality product of gained is high, low toxic and environment-friendly, and the tin content in the prescription is less, is applicable to all kinds of hard sheet material of PVC, has excellent initial and long-term thermal stability, and the goods transparency is high.
2, the preparation method of composite thermal stabilizer is simple, stable process conditions, and control is easy to suitability for industrialized production easily, the simple environmental protection of technical process, raw material is easy to get, and the consumption of rare metal tin reduces, and reduces production costs, and improves the market competitiveness.
(4) embodiment
Below in conjunction with specific embodiment preparation method of the present invention is described further, but protection scope of the present invention is not limited thereto.
Preparation Thiovanic acid methyl tin: the mixture of 100kg dimethyltin chloride and monomethyl tindichloride (wherein the mass ratio of dimethyltin chloride and monomethyl tin trichloride is 80: 20) (east, Hangzhou rising sun auxiliary agent ltd produces), 108kg Thiovanic acid (production of Shandong Weifang Yihua Chemical Co., Ltd.) and 300kg water mix under 70 ℃ of temperature; Stir, the ammoniacal liquor that adds 25wt% is regulated pH value 7, reacts 5 hours; Filter; Underpressure distillation makes the S of 172kg, S '-two (Thiovanic acid) tin methide and S; S ' S " mixture of-three (Thiovanic acid) monomethyl tin, be Thiovanic acid methyl tin.
Embodiment 1
Get Thiovanic acid methyl tin 10kg and tri-thiol 2-ethyl hexyl ethanoate antimony 40kg respectively, mix and the input reaction kettle, the control stirring velocity is at 80r/min; Controlled temperature is at 65 ℃, is mixed, soaking time is 0.5h, drops into isocaprylic acid zinc 5kg again; Mix 1h; Cool off then, filter and obtain colourless transparent liquid Sn-Sb-Zn Methyltin composite heat stabilizer 55kg, detect wherein tin content, see table 1.
Embodiment 2
Get Thiovanic acid methyl tin 15kg and five isooctyl mercaptoacetate antimony 45kg respectively, mix and the input reaction kettle, the control stirring velocity is at 90r/min; Controlled temperature is at 75 ℃, is mixed, soaking time is 1h, drops into isocaprylic acid zinc 10kg again; Mix 1h; Cool off then, filter and obtain colourless transparent liquid Sn-Sb-Zn Methyltin composite heat stabilizer 70kg, detect wherein tin content, see table 1.
Embodiment 3
Get Thiovanic acid methyl tin 17kg and five ethyl thioglycolate antimony 50kg respectively, mix and the input reaction kettle, the control stirring velocity is at 100r/min; Controlled temperature is at 85 ℃, is mixed, soaking time is 1.5h, drops into zinc oleate 15kg again; Mix 1.5h; Cool off then, filter and obtain colourless transparent liquid Sn-Sb-Zn Methyltin composite heat stabilizer 82kg, detect wherein tin content, see table 1.
Embodiment 4
Get Thiovanic acid methyl tin 12kg and tri-thiol 2-ethyl hexyl ethanoate antimony 43kg respectively, mix and the input reaction kettle, the control stirring velocity is at 115r/min; Controlled temperature is at 110 ℃, is mixed, soaking time is 2h, drops into zinc oleate 6kg again; Mix 1.5h; Cool off then, filter and obtain colourless transparent liquid Sn-Sb-Zn Methyltin composite heat stabilizer 61kg, detect wherein tin content, see table 1.
Embodiment 5
Get Thiovanic acid methyl tin 16kg and five isooctyl mercaptoacetate antimony 55kg respectively, mix and the input reaction kettle, the control stirring velocity is at 135r/min; Controlled temperature is at 115 ℃, is mixed, soaking time is 2.5h, drops into p-tert-butyl benzoic acid zinc 8kg again; Mix 2h; Cool off then, filter and obtain colourless transparent liquid Sn-Sb-Zn Methyltin composite heat stabilizer 79kg, detect wherein tin content, see table 1.
Embodiment 6
Get Thiovanic acid methyl tin 20kg and tri-thiol ETHYLE ACETATE antimony 60kg respectively, mix and the input reaction kettle, the control stirring velocity is at 150r/min; Controlled temperature is at 120 ℃; Be mixed, soaking time is 3h, drops into p-tert-butyl benzoic acid zinc 15kg again, mix 2h and cool off then, filter and obtain colourless transparent liquid Sn-Sb-Zn Methyltin composite heat stabilizer 95kg; Detect wherein tin content, see table 1.
Performance test:
Get the Methyltin composite heat stabilizer that embodiment 1～6 makes; Process the PVC sample according to following material formula; Be designated as coupons 1～coupons 6 respectively; And get commercially available sheet material and use the methyl tin heat stabilizer: import methyl tin 181 and homemade methyl tin 181, process PVC sheet material sample respectively according to same prescription, as contrast.Thermal stability by following method test PVC sample.
Static heat stability:
According to the PVC prescription, accurately take by weighing each component, mixing of materials is even with experiment with mixing machine; Mixing on open type plastic purificating set, temperature is 190 ± 2 ℃, and mixing time is approximately 3min; Process the coupons that thickness is about 1mm, detect the transmittance of each coupons, the result sees table 1.Each coupons is carried out the heat baking under 185 ± 2 ℃ of temperature.Static heat steady time: the time of PVC coupons blackening, the result sees table 1.
The dynamic thermal stability ability:
According to the PVC accurate weighing PVC compound of filling a prescription, join torque rheometer and carry out the rheological behaviour test, the record rheological data.Experiment condition: the milling device temperature is 185 ℃, and spinner velocity is 40r/min.Dynamically heat-stable time: PVC is from plastifying to the time of decomposing.The result sees table 2.
PVC sheet material basic components (PHR):
PVC (SG-7) (Qilu Co., Ltd., China Petrochemical Corp): 100g; Methyl tin heat stabilizer: 1.1g; DOP (Qilu Co., Ltd., China Petrochemical Corp): 2g, G16 (Zhejiang Hai Pudun novel material limited-liability company): 0.8g, G70S (Zhejiang Hai Pudun novel material limited-liability company): 0.4g; MBS (Japanese Zhong Yuan company): 5g, ACR-401 (Shandong Rui Feng macromolecular material limited-liability company): 1g.
Table 1 various sample sheet static heat stability
Table 2 various sample dynamic thermal stability ability
| Stablizer | Dynamic heat-stable time (min) | Processing moment of torsion (Nm) |
| Coupons 1 | 24.7 | 12.2 |
| Coupons 2 | 25.0 | 12.6 |
| Coupons 3 | 24.8 | 12.5 |
| Coupons 4 | 25.1 | 12.2 |
| Coupons 5 | 25.0 | 12.4 |
| Coupons 6 | 25.1 | 12.6 |
| Import 181 | 25.3 | 14.5 |
| Homemade 181 | 24.7 | 14.2 |
Can find out that from experimental data the PVC sheet material that the present invention makes is compared with the commercial like product with the Sn-Sb-Zn composite thermal stabilizer, tin content significantly reduces, and gives the good thermostability of PVC sheet material products, the transparency and processing characteristics.
Claims (7)
1. a PVC sheet material is used the Sn-Sb-Zn composite thermal stabilizer, it is characterized in that said PVC sheet material comprises the component of following weight part with the Sn-Sb-Zn composite thermal stabilizer:
10～20 parts in Thiovanic acid methyl tin
40～60 parts in mercaptoacetate antimony
5～15 parts of organic acid zinc salts
Described Thiovanic acid methyl tin is S; S '-two (Thiovanic acid) tin methide and S; S ' S " mixture of-three (Thiovanic acid) monomethyl tin; being under alkaline condition, is that 80: 20 the dimethyltin chloride and the mixture and the Thiovanic acid of monomethyl tin trichloride prepare with esterification process by mass ratio;
Said mercaptoacetate antimony is any one shown in formula III;
In the formula III, R
1Be the straight chain saturated alkyl of C2-C8, n=3 or 5;
Said organic acid zinc salt is a zinc oleate, any one in isocaprylic acid zinc or the p-tert-butyl benzoic acid zinc.
2. PVC sheet material as claimed in claim 1 is used the Sn-Sb-Zn composite thermal stabilizer, it is characterized in that said PVC sheet material is made up of the component of following weight part with the Sn-Sb-Zn composite thermal stabilizer:
10～20 parts in Thiovanic acid methyl tin
40～60 parts in mercaptoacetate antimony
5～15 parts of organic acid zinc salts.
3. according to claim 1 or claim 2 PVC sheet material is used the Sn-Sb-Zn composite thermal stabilizer; It is characterized in that said Thiovanic acid methyl tin makes by following method: under alkaline condition, be the mixture of 80: 20 methyl dichloro tin and monomethyl tin trichloride, mix with mass ratio 1: 1～1.1: 3～4 with Thiovanic acid and water again by mass ratio; Under 60～80 ℃ of temperature; Using ammoniacal liquor to regulate the pH value is 7～8, reacts 2～5 hours after-filtration, and underpressure distillation obtains said Thiovanic acid methyl tin.
4. according to claim 1 or claim 2 PVC sheet material is used the Sn-Sb-Zn composite thermal stabilizer, it is characterized in that described mercaptoacetate antimony is any one in tri-thiol 2-ethyl hexyl ethanoate antimony, five isooctyl mercaptoacetate antimony, tri-thiol ETHYLE ACETATE antimony or the five ethyl thioglycolate antimony.
5. according to claim 1 or claim 2 PVC sheet material is used the Sn-Sb-Zn composite thermal stabilizer; It is characterized in that said PVC sheet material prepares by following method with the Sn-Sb-Zn composite thermal stabilizer:, Thiovanic acid methyl tin and mercaptoacetate antimony are mixed control stirring velocity 80～150r/min according to the feed composition proportioning; Controlled temperature is at 65～120 ℃; Behind reaction 0.5～3h, drop into the organic acid zinc salt again and mix 1-2h, be cooled to room temperature then; Filter, getting filtrating and being said PVC sheet material and using the Sn-Sb-Zn composite thermal stabilizer.
6. PVC sheet material as claimed in claim 1 is with the application of Sn-Sb-Zn composite thermal stabilizer as the PVC thermo-stabilizer.
7. application as claimed in claim 6 is characterized in that the method for said application is: the PVC sheet material that adds 0.8 part～1.2 mass parts in the SE of per 100 mass parts with the Sn-Sb-Zn composite thermal stabilizer as thermo-stabilizer.
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Cited By (8)
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| CN105038038A (en) * | 2015-09-07 | 2015-11-11 | 太仓金昊达新材料有限公司 | PVC composite plastic particle |
| CN105968411A (en) * | 2016-06-27 | 2016-09-28 | 浙江海普顿新材料股份有限公司 | One-pot methyltin mercaptide composite heat stabilizer preparation method |
| CN106084288A (en) * | 2016-06-16 | 2016-11-09 | 浙江海普顿新材料股份有限公司 | A kind of mercaptans type composite thermal stabilizer and preparation method thereof |
| CN106188144A (en) * | 2016-07-20 | 2016-12-07 | 浙江海普顿新材料股份有限公司 | A kind of liquid organotin antimonial and its preparation method and application |
| CN106633182A (en) * | 2016-10-10 | 2017-05-10 | 台州联成化工有限公司 | Transparent heat stabilizer and method for preparing same |
| CN108250608A (en) * | 2017-11-29 | 2018-07-06 | 广德粤华塑业制品有限公司 | A kind of environment-friendly PVC plastic cement stabilization agent |
| CN108250678A (en) * | 2017-11-29 | 2018-07-06 | 广德粤华塑业制品有限公司 | A kind of environment-friendly PVC section bar organic tin stabilizer |
| CN109776863A (en) * | 2019-02-22 | 2019-05-21 | 台州联成化工有限公司 | Liquid-transparent heat stabilizer for PVC product |
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| CN102153824A (en) * | 2011-04-20 | 2011-08-17 | 山东慧科助剂股份有限公司 | Environmental-friendly high-efficiency composite heat stabilizer for tribasic zinc PVC (polyvinyl chloride) and preparation method of environmental-friendly high-efficiency composite heat stabilizer |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038038A (en) * | 2015-09-07 | 2015-11-11 | 太仓金昊达新材料有限公司 | PVC composite plastic particle |
| CN106084288A (en) * | 2016-06-16 | 2016-11-09 | 浙江海普顿新材料股份有限公司 | A kind of mercaptans type composite thermal stabilizer and preparation method thereof |
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| CN106188144A (en) * | 2016-07-20 | 2016-12-07 | 浙江海普顿新材料股份有限公司 | A kind of liquid organotin antimonial and its preparation method and application |
| CN106633182A (en) * | 2016-10-10 | 2017-05-10 | 台州联成化工有限公司 | Transparent heat stabilizer and method for preparing same |
| CN108250608A (en) * | 2017-11-29 | 2018-07-06 | 广德粤华塑业制品有限公司 | A kind of environment-friendly PVC plastic cement stabilization agent |
| CN108250678A (en) * | 2017-11-29 | 2018-07-06 | 广德粤华塑业制品有限公司 | A kind of environment-friendly PVC section bar organic tin stabilizer |
| CN109776863A (en) * | 2019-02-22 | 2019-05-21 | 台州联成化工有限公司 | Liquid-transparent heat stabilizer for PVC product |
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Application publication date: 20120919 |