CN102731927A - Methyl tin composite heat stabilizer used for PVC rigid pipes, its preparation method and application - Google Patents
Methyl tin composite heat stabilizer used for PVC rigid pipes, its preparation method and application Download PDFInfo
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- CN102731927A CN102731927A CN2012101971583A CN201210197158A CN102731927A CN 102731927 A CN102731927 A CN 102731927A CN 2012101971583 A CN2012101971583 A CN 2012101971583A CN 201210197158 A CN201210197158 A CN 201210197158A CN 102731927 A CN102731927 A CN 102731927A
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- dodecyl mercaptan
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Abstract
The invention discloses a methyl tin composite heat stabilizer used for PVC (polyvinyl chloride) rigid pipes, and the composite heat stabilizer comprises the following components by weight: 30-40 parts of N-dodecyl mercaptan methyl tin, 10-15 parts of synergist A, 10-15 parts of synergist B, and 5-10 parts of an antioxidizer. The invention also discloses the preparation method of the composite heat stabilizer and its application as a PVC heat stabilizer. The composite heat stabilizer obtained in the invention is characterized by high product quality, low toxicity and environmental protection, less tin content in the formula, applicability to various PVC rigid pipes, as well as excellent heat stability and processability.
Description
(1) technical field
The present invention relates to plastic processing technology, more particularly relate to a kind of PVC hard tubing with Methyltin composite heat 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.
The methyl tin heat stabilizer of existing market is single variety; And different PVC goods are (like sheet material; Film, pipe profile etc.) the thermo-stabilizer performance demands is had nothing in common with each other, therefore, develop the special-purpose methyl tin heat stabilizer of different PVC goods; Satisfy different requirements of customers, can significantly improve the competitiveness of product in market.
(3) summary of the invention
To the problem that methyl tin stabilizer in the prior art exists, the present invention provides a kind of PVC hard tubing to use Methyltin composite heat stabilizer, 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 thermostability of PVC stereoplasm tube material products;
3, further improve the processing characteristics of PVC hard tubing;
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 hard tubing is used Methyltin composite heat stabilizer, it is characterized in that said PVC hard tubing comprises the component of following weight part with Methyltin composite heat stabilizer:
Described positive Dodecyl Mercaptan methyl tin is S; S '-two (positive Dodecyl Mercaptan) tin methide and S; S ' S " mixture of-three (positive Dodecyl Mercaptan) monomethyl tin; being under alkaline condition, is that the mixture of dimethyltin chloride and the monomethyl tin trichloride of 80:20 prepares with esterification process with Dodecyl Mercaptan just by mass ratio;
Said synergistic agent A is butyl stearate, methyl stearate, butyl oleate or pentaerythritol oleate;
Said synergistic agent B is white oil or tasteless kerosene;
Described oxidation inhibitor is phosphite ester kind antioxidant, and promptly phosphite ester compound is an oxidation inhibitor.
Further, PVC hard tubing according to the invention is made up of the component of following weight part with Methyltin composite heat stabilizer:
Positive Dodecyl Mercaptan methyl tin according to the invention can make by following method: under alkaline condition; By mass ratio is the mixture of 80:20 dimethyltin chloride and monomethyl tin trichloride; Mix with mass ratio 1:2.4 ~ 2.6:3 ~ 4 with positive Dodecyl Mercaptan and water, under 60 ~ 80 ℃ of temperature, using ammoniacal liquor to regulate the pH value is 7 ~ 8 again; React 2 ~ 5 hours after-filtration, underpressure distillation obtains the positive Dodecyl Mercaptan methyl of said sulphur tin.This is to well known to a person skilled in the art the esterification preparation method.
Prepared positive Dodecyl Mercaptan methyl tin is suc as formula the S shown in the I, S '-two (positive Dodecyl Mercaptan) tin methide and suc as formula the S shown in the II, S ' S " mixture of-three (positive Dodecyl Mercaptan) monomethyl tin:
Oxidation inhibitor of the present invention is diisooctyl phenyl phosphite, isooctyl diphenyl phosphite, phosphorous acid one benzene, two isodecyl esters or phosphorous acid hexichol isodecyl ester.
PVC hard tubing according to the invention prepares by following method with Methyltin composite heat stabilizer:, positive Dodecyl Mercaptan methyl tin and oxidation inhibitor are mixed control stirring velocity 80 ~ 150r/min according to the feed composition proportioning; Controlled temperature is at 65 ~ 120 ℃, and behind reaction 1 ~ 2h, dropping into has synergistic agent A and synergistic agent B again; Mix 0.5-3h; Be cooled to room temperature then, filter, getting filtrating and being said PVC hard tubing and using Methyltin composite heat stabilizer.
PVC hard tubing of the present invention can be used the thermo-stabilizer as PVC with Methyltin composite heat stabilizer; Concrete; The method of said application is: the PVC hard tubing of adding 0.5 part～1.0 mass parts as thermo-stabilizer, is used to prepare PVC hard tubing with Methyltin composite heat stabilizer in the SE of per 100 mass parts.
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 tubing of PVC, has excellent thermostability and processing characteristics.
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) description of drawings
The processing flow curve figure of the different methyl tin heat stabilizers of Fig. 1
(5) 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.
Prepare positive Dodecyl Mercaptan methyl tin: the mixture of 100kg dimethyltin chloride and monomethyl tin trichloride (wherein the mass ratio of dimethyltin chloride and monomethyl tin trichloride is 80:20) (east, Hangzhou rising sun auxiliary agent ltd produces), positive Dodecyl Mercaptan of 250kg (Jinan friendship ties chemical industry ltd) and 300kg water mix under 70 ℃ of temperature; Stir, the ammoniacal liquor that adds 25wt% is regulated pH value 7 ~ 8, reacts 5 hours; Filter; Underpressure distillation makes the S of 300kg, S '-two (positive Dodecyl Mercaptan) tin methide and S; S ' S " mixture of-three (positive Dodecyl Mercaptan) monomethyl tin, be positive Dodecyl Mercaptan methyl tin.
Embodiment 1
Get the positive Dodecyl Mercaptan methyl of 30kg tin respectively, 10kg butyl stearate and 10kg white oil mix and the input reaction kettle; The control stirring velocity is at 80r/min, and controlled temperature is at 65 ℃, is mixed, soaking time is 1h; Drop into the 5kg diisooctyl phenyl phosphite again, mix 0.5h, cool off then, filter and obtain PVC hard tubing and use Methyltin composite heat stabilizer 55kg; Detect wherein tin content, see table 1.
Embodiment 2
Get the positive Dodecyl Mercaptan methyl of 32kg tin respectively, 11kg methyl stearate and 12kg tasteless kerosene mix and the input reaction kettle; The control stirring velocity is at 100r/min, and controlled temperature is at 75 ℃, is mixed, soaking time is 1h; Drop into the 6kg isooctyl diphenyl phosphite again, mix 1.5h, cool off then, filter and obtain PVC hard tubing and use Methyltin composite heat stabilizer 61kg; Detect wherein tin content, see table 1.
Embodiment 3
Get the positive Dodecyl Mercaptan methyl of 34kg tin respectively, 13kg butyl oleate and 11kg white oil mix and the input reaction kettle; The control stirring velocity is at 110r/min, and controlled temperature is at 80 ℃, is mixed, soaking time is 1.5h; Drop into 7kg phosphorous acid one benzene two isodecyl esters again, mix 2.5h, cool off then, filter and obtain PVC hard tubing and use Methyltin composite heat stabilizer 65kg; Detect wherein tin content, see table 1.
Embodiment 4
Get the positive Dodecyl Mercaptan methyl of 36kg tin respectively, 12kg pentaerythritol oleate and 14kg tasteless kerosene mix and the input reaction kettle; The control stirring velocity is at 120r/min, and controlled temperature is at 90 ℃, is mixed, soaking time is 1.5h; Drop into 9kg phosphorous acid hexichol isodecyl ester again, mix 1h, cool off then, filter and obtain PVC hard tubing and use Methyltin composite heat stabilizer 71kg; Detect wherein tin content, see table 1.
Embodiment 5
Get the positive Dodecyl Mercaptan methyl of 38kg tin respectively, 13kg methyl stearate and 12kg tasteless kerosene mix and the input reaction kettle; The control stirring velocity is at 130r/min, and controlled temperature is at 115 ℃, is mixed, soaking time is 2h; Drop into the 8kg isooctyl diphenyl phosphite again, mix 2h, cool off then, filter and obtain PVC hard tubing and use Methyltin composite heat stabilizer 71kg; Detect wherein tin content, see table 1.
Embodiment 6
Get positive Dodecyl Mercaptan methyl tin 40kg respectively, 15kg butyl oleate and 15kg white oil mix and the input reaction kettle; The control stirring velocity is at 150r/min, and controlled temperature is at 120 ℃, is mixed, soaking time is 2h; Drop into 10kg phosphorous acid one benzene two isodecyl esters again, mix 3h, cool off then, filter and obtain PVC hard tubing and use Methyltin composite heat stabilizer 80kg; Detect wherein tin content, see table 1.
Performance test:
Process the PVC sample according to following pvc pipe material basic components; The methyl tin heat stabilizer is got the Methyltin composite heat stabilizer that embodiment 1 ~ 6 makes respectively; Be designated as coupons 1 ~ coupons 6; And get commercially available methyl tin heat stabilizer: homemade methyl tin 181 (the eastern rising sun), process the PVC sample according to same prescription, as control sample.
Pvc pipe material basic components (PHR):
PVC (SG-5) (Qilu Co., Ltd., China Petrochemical Corp): 100g, methyl tin heat stabilizer: 0.6g, OPE (U.S. Honeywell Inc.): 0.3g, Triple Pressed Stearic Acid 1801 (Indonesia, import): 0.3g; ACR-401:1.2g, CPE (Shandong Weifang Yaxing Chemical Co., Ltd.): 1g, TiO
2(Zhenjiang white titanium pigment limited-liability company): 1.8g; Lightweight CaCO
3(Jiande City is the meticulous calcium industry of hall ltd by the emperor himself): 25g.
Thermal stability and processing characteristics by following method test PVC sample.
Static heat stability:
According to the PVC prescription, accurately take by weighing each component, with mixing machine that mixing of materials is even with experiment, mixing on open type plastic purificating set, temperature is 190 ± 2 ℃, mixing time is approximately 3min, processes the coupons that thickness is about 1mm.Each coupons is carried out heat baking under 185 ± 2 ℃ of temperature, static heat steady time: the time of PVC coupons blackening, the result sees table 1.
Processing characteristics:
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.The gained result sees Fig. 1, and the methyl composite thermal stabilizer is the Methyltin composite heat stabilizer that embodiment 1 makes among Fig. 1.
Table 1 various sample sheet static heat stability
Can find out that from above experimental data the PVC hard tubing that the present invention makes is compared with the commercial like product with Methyltin composite heat stabilizer, tin content significantly reduces, and has good thermostability and processing characteristics.
Claims (7)
1. a PVC hard tubing is used Methyltin composite heat stabilizer, it is characterized in that said PVC hard tubing comprises the component of following weight part with Methyltin composite heat stabilizer:
Described positive Dodecyl Mercaptan methyl tin is S; S '-two (positive Dodecyl Mercaptan) tin methide and S; S ' S " mixture of-three (positive Dodecyl Mercaptan) monomethyl tin; being under alkaline condition, is that the mixture of dimethyltin chloride and the monomethyl tin trichloride of 80:20 prepares with esterification process with Dodecyl Mercaptan just by mass ratio;
Said synergistic agent A is butyl stearate, methyl stearate, butyl oleate or pentaerythritol oleate;
Said synergistic agent B is white oil or tasteless kerosene;
Described oxidation inhibitor is phosphite ester kind antioxidant.
2. PVC hard tubing as claimed in claim 1 is used Methyltin composite heat stabilizer, it is characterized in that said pvc pipe material is made up of the component of following weight part with Methyltin composite heat stabilizer:
3. according to claim 1 or claim 2 PVC hard tubing is used Methyltin composite heat stabilizer; It is characterized in that said positive Dodecyl Mercaptan methyl tin makes by following method: under alkaline condition, be the mixture of 80:20 dimethyltin chloride and monomethyl tin trichloride, mix with mass ratio 1:2.4 ~ 2.6:3 ~ 4 with positive Dodecyl Mercaptan 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 positive Dodecyl Mercaptan methyl tin.
4. according to claim 1 or claim 2 PVC hard tubing is used Methyltin composite heat stabilizer, it is characterized in that described oxidation inhibitor is diisooctyl phenyl phosphite, isooctyl diphenyl phosphite, phosphorous acid one benzene, two isodecyl esters or phosphorous acid hexichol isodecyl ester.
5. according to claim 1 or claim 2 PVC hard tubing is used Methyltin composite heat stabilizer, it is characterized in that said pvc pipe material prepares by following method with Methyltin composite heat stabilizer:, positive Dodecyl Mercaptan methyl tin and oxidation inhibitor are mixed according to the feed composition proportioning; Control stirring velocity 80 ~ 150r/min; Controlled temperature is at 65 ~ 120 ℃, and behind reaction 1 ~ 2h, dropping into has synergistic agent A and synergistic agent B again; Mix 0.5-3h; Be cooled to room temperature then, filter, getting filtrating and being said PVC hard tubing and using Methyltin composite heat stabilizer.
6. PVC hard tubing as claimed in claim 1 is with the application of Methyltin composite heat stabilizer as the PVC thermo-stabilizer.
7. application as claimed in claim 6; The method that it is characterized in that said application is: the PVC hard tubing of adding 0.5 part～1.0 mass parts as thermo-stabilizer, is used to prepare PVC hard tubing with Methyltin composite heat stabilizer in the SE of per 100 mass parts.
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| CN2012101971583A CN102731927A (en) | 2012-06-14 | 2012-06-14 | Methyl tin composite heat stabilizer used for PVC rigid pipes, its preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105218972A (en) * | 2015-10-13 | 2016-01-06 | 云南锡业股份有限公司 | A kind of polyvinyl chloride card specific complex thermo-stabilizer and preparation method thereof |
| CN106589687A (en) * | 2016-12-09 | 2017-04-26 | 郑州搜趣信息技术有限公司 | Heat stabilizer for polyvinyl chloride and preparation method of heat stabilizer |
| CN114516996A (en) * | 2022-03-28 | 2022-05-20 | 金发科技股份有限公司 | Boiling-resistant PVC alloy material and preparation method and application thereof |
| CN114516997A (en) * | 2022-03-28 | 2022-05-20 | 金发科技股份有限公司 | High-heat-resistance flame-retardant PVC alloy composition and preparation method and application thereof |
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| US4179432A (en) * | 1975-09-02 | 1979-12-18 | Cincinnati Milacron Chemicals, Inc. | Stabilized polypropylene compositions |
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| US4179432A (en) * | 1975-09-02 | 1979-12-18 | Cincinnati Milacron Chemicals, Inc. | Stabilized polypropylene compositions |
| CN101864186A (en) * | 2009-04-15 | 2010-10-20 | 罗门哈斯公司 | The polymer composition of stabilization |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105218972A (en) * | 2015-10-13 | 2016-01-06 | 云南锡业股份有限公司 | A kind of polyvinyl chloride card specific complex thermo-stabilizer and preparation method thereof |
| CN106589687A (en) * | 2016-12-09 | 2017-04-26 | 郑州搜趣信息技术有限公司 | Heat stabilizer for polyvinyl chloride and preparation method of heat stabilizer |
| CN114516996A (en) * | 2022-03-28 | 2022-05-20 | 金发科技股份有限公司 | Boiling-resistant PVC alloy material and preparation method and application thereof |
| CN114516997A (en) * | 2022-03-28 | 2022-05-20 | 金发科技股份有限公司 | High-heat-resistance flame-retardant PVC alloy composition and preparation method and application thereof |
| CN114516997B (en) * | 2022-03-28 | 2023-08-22 | 金发科技股份有限公司 | High heat-resistant flame-retardant PVC alloy composition and preparation method and application thereof |
| CN114516996B (en) * | 2022-03-28 | 2023-08-22 | 金发科技股份有限公司 | Boiling-resistant PVC alloy material and preparation method and application thereof |
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Application publication date: 20121017 |