CN102260379A - composite heat stabilizer and method for processing chlorine-containing polymer - Google Patents
composite heat stabilizer and method for processing chlorine-containing polymer Download PDFInfo
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- CN102260379A CN102260379A CN 201010182474 CN201010182474A CN102260379A CN 102260379 A CN102260379 A CN 102260379A CN 201010182474 CN201010182474 CN 201010182474 CN 201010182474 A CN201010182474 A CN 201010182474A CN 102260379 A CN102260379 A CN 102260379A
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Abstract
The invention relates to a composite heat stabilizer which comprises the following components by mass, 10%-30% of ethylene diamine tetraacetic acid, citric acid or other compositions, 0-30% of epoxy soybean oil and 40%-80% of organotin heat stabilizer. The invention also provides a method for processing a chlorine-containing polymer. The composite heat stabilizer has the advantages of nontoxicity, reduced cost and good stability.
Description
Technical field
The present invention relates to the working method of a kind of thermo-stabilizer and chlorine-containing polymer, especially a kind of composite thermal stabilizer and adopt the working method of the chlorine-containing polymer of this composite thermal stabilizer.
Background technology
Now, the application of chlorine-containing polymer is very extensive.With polyvinyl chloride (PVC) is example, because it has superior corrosion resistance and preferable mechanical property, and has advantages such as cheap, abundant raw material, manufacturing process maturation, has been widely used in the every field of industrial and agricultural production.
Add man-hour at polyvinyl chloride, need it is heated.Yet, owing to have defective in the polrvinyl chloride structure, cause it when being heated to 110 ℃, just can deviate from hydrogenchloride, and hydrogenchloride also can quicken the polyvinyl chloride decomposition; Therefore obvious degradation can take place in polyvinyl chloride when 160～200 ℃ processing temperature, thereby causes the product variable color and reduce mechanical performance of products, influences the work-ing life of product.
Add the problem of decomposing easily man-hour for solving polyvinyl chloride, can add at polyvinyl chloride usually in the prior art and add thermo-stabilizer man-hour.The main effect of using thermo-stabilizer to play in polyvinyl chloride processing has: by replacing unsettled chlorine atom, absorbing hydrogen chloride and the degraded that mode such as addition reaction suppresses the polyvinyl chloride molecule taking place with unsaturated position.
Thermo-stabilizer commonly used has lead salts stablizer, organo-tin het stabilizer and metal soap thermal stabilizers etc. in the polyvinyl chloride processing.Wherein, the lead salts stablizer is the thermo-stabilizer that polyvinyl chloride uses the earliest, and its cost is low, have good thermostability, but has toxicity, consistency and dispersed relatively poor.Organo-tin het stabilizer stability is comparatively excellent, but cost is higher.Metal soap thermal stabilizers uses with multiple metallic soap compound form usually, have the advantage of environmental protection, but its shortcoming is a large usage quantity, and less stable.
In view of above-mentioned condition, be necessary to provide the working method of a kind of composite thermal stabilizer that addresses the above problem and chlorine-containing polymer.
Summary of the invention
The present invention proposes a kind of composite thermal stabilizer, and it is nontoxic, can reduce cost and have preferable stability.
The present invention also proposes a kind of working method of chlorine-containing polymer, its can improve chlorine-containing polymer the course of processing stability and reduce cost.
A kind of composite thermal stabilizer, in mass, it comprises 10～30% ethylenediamine tetraacetic acid (EDTA), citric acid or its composition, 0～30% epoxy soybean oil, and 40～80% organo-tin het stabilizers.
A kind of working method of chlorine-containing polymer, it may further comprise the steps.At first be mixed in proportion chlorine-containing polymer and composite thermal stabilizer to form mixture.In mass, this composite thermal stabilizer comprises 10～30% ethylenediamine tetraacetic acid (EDTA), citric acid or its composition, 0～30% epoxy soybean oil, and 40～80% organo-tin het stabilizers.Heat this mixture then.Wherein, the usage quantity of composite thermal stabilizer in mass, can account for 4～8% of chlorine-containing polymer.
The epoxy soybean oil of ethylenediamine tetraacetic acid (EDTA), citric acid or its composition and 0～30% of above-mentioned composite thermal stabilizer employing 10～30%, be used with organo-tin het stabilizer, therefore guaranteeing that composite thermal stabilizer has under preferable stability and the nontoxic prerequisite, also can reduce cost.
Embodiment
Below in conjunction with embodiment the working method of composite thermal stabilizer of the present invention and chlorine-containing polymer is described in further detail.
The composite thermal stabilizer of the embodiment of the invention, in mass, it can comprise the mixture of 10～30% ethylenediamine tetraacetic acid (EDTA) (EDTA) and citric acid, 0～30% epoxy soybean oil, and 40～80% organo-tin het stabilizers.In the mixture of composite thermal stabilizer ethylenediamine tetraacetic acid (EDTA) or citric acid, the quality percentage composition of ethylenediamine tetraacetic acid (EDTA) can be 8～20%, and the quality percentage composition of citric acid can be 2～10%.Organo-tin het stabilizer can be toxilic acid tin alkyl, thio-alcohol organotin etc., for example (CH
3)
2Sn (SCH
2COOC
8H
17)
2Preferably, organo-tin het stabilizer can be 60～80% at the quality percentage composition in composite thermal stabilizer.In addition, epoxy soybean oil can be commercially available soybean oil, for example is the product of Guangzhou Dongfeng Chemical Industrial Co., Ltd..It is to be noted, in other embodiments of the invention, can only comprise one of them of ethylenediamine tetraacetic acid (EDTA) (EDTA) and citric acid in the composite thermal stabilizer, and this moment ethylenediamine tetraacetic acid (EDTA) the quality percentage composition can be 10～30%, the quality percentage composition of citric acid can be 10～30%.
In the above-mentioned composite thermal stabilizer, adopt 10～30% ethylenediamine tetraacetic acid (EDTA), citric acid or its composition, 0～30% epoxy soybean oil and organo-tin het stabilizer to be used, therefore guaranteeing that composite thermal stabilizer has under preferable stability and the nontoxic prerequisite, also can reduce cost.
A kind of working method of chlorine-containing polymer, it is above-mentioned composite thermal stabilizer to be mixed with chlorine-containing polymer to form mixture earlier, and then heats this mixture.The mixture of heating can be used for moulding or is processed into the product with required shapes/configurations.Wherein, chlorine-containing polymer can be one of polyvinyl chloride (PVC), chlorinatedpolyethylene, chlorinated polyvinyl chloride, vinyl chloride-ethylene copolymer and vinyl chloride acetate copolymer or its composition.In this mixture, in mass, the consumption of composite thermal stabilizer can be 4～8% of chlorine-containing polymer.And for ease of the moulding and the processing of chlorine-containing polymer, this mixture also can be mixed with dioctyl phthalate (DOP) (DOP), polyethylene wax (PE wax), calcium stearate or Zinic stearas etc. as additive.For example, in mass, the consumption of dioctyl phthalate (DOP) be chlorine-containing polymer 0～65%, the consumption of polyethylene wax be chlorine-containing polymer 0.4～1%, the calcium stearate consumption is 0～5% of this chlorine-containing polymer, and the Zinic stearas consumption is in half of calcium stearate consumption.
In the working method of above-mentioned chlorine-containing polymer because the composite thermal stabilizer that adopts has preferable stability and lower cost, therefore can improve chlorine-containing polymer the course of processing stability and cut down finished cost.Particularly, for example in the above-mentioned course of processing, under 180 ± 1 ℃ environment, the heat-stable time of chlorine-containing polymer can reach more than 60 minutes.
Have preferable stability for further specifying above-mentioned composite thermal stabilizer, and the working method of above-mentioned chlorine-containing polymer can improve the stability of the course of processing of chlorine-containing polymer, below will enumerate specific embodiment and be further described.
By prescription shown in the table 1 (wherein fill a prescription and calculate), take by weighing each component earlier and mix the formation mixture with mass fraction.Then this mixture is placed on the double roller plastic-making device of about 160 ℃ of roller temperature, 1 millimeter of roll spacing and plasticated 5 minutes.Sheet promptly gets samples of sheets under after the plasticizing fully.According to standard GB/T 9349-2002, adopt the test of oven heat method.Earlier the samples of sheets that makes is cut into the shape of 2 centimetres of sizes of 2 cm x and puts into porcelain dish, then porcelain dish is put into 180 ± 1 ℃ baking oven observation sample variable color situation.In the test result, the corresponding variable color time of each samples of sheets is as shown in table 1.
Table 1 sample compositing formula and variable color time thereof
| Sequence number | PVC | DOP | PE wax | Calcium stearate | Zinic stearas | Organo-tin het stabilizer | EDTA | Citric acid | Epoxy soybean oil | The variable color time (min) |
| 1 | 100 | - | 0.5 | - | - | 1.6 | - | 1.2 | 1.2 | 60 |
| 2 | 100 | - | 0.5 | - | - | 1.6 | 1.2 | - | 1.2 | 70 |
| 3 | 100 | - | 0.5 | - | - | 1.6 | 0.6 | 0.6 | 1.2 | 70 |
| 4 | 100 | - | 0.5 | - | - | 2 | - | 1.5 | 1.5 | 70 |
| 5 | 100 | - | 0.5 | - | - | 2 | 1.5 | - | 1.5 | 90 |
| 6 | 100 | - | 0.5 | - | - | 2 | 0.75 | 0.75 | 1.5 | 80 |
| 7 | 100 | - | 0.5 | - | - | 3 | - | 0.5 | 1.5 | 100 |
| 8 | 100 | - | 0.5 | - | - | 3 | 0.5 | - | 1.5 | 110 |
| 9 | 100 | - | 0.5 | - | - | 3 | 0.85 | 0.4 | 0.75 | 100 |
| 10 | 100 | - | 0.5 | - | - | 3 | 0.4 | 0.5 | 1.1 | 100 |
| 11 | 100 | - | 0.5 | - | - | 3 | 1 | 0.5 | 1.5 | 120 |
| 12 | 100 | - | 0.5 | - | - | 3.5 | 0.5 | 0.1 | 0.9 | 150 |
| 13 | 100 | - | 0.5 | - | - | 3.5 | 0.9 | 0.3 | 0.3 | 140 |
| 14 | 100 | - | 0.5 | - | - | 4 | 0.5 | 0.5 | - | 170 |
| 15 | 100 | - | 0.5 | - | - | 4 | 0.3 | 0.7 | - | 160 |
| 16 | 100 | 30 | - | - | - | 2 | 1.5 | 0.9 | 0.6 | 90 |
| 17 | 100 | 30 | - | - | - | 3 | 0.5 | - | 1.5 | 110 |
| 18 | 100 | - | 0.5 | - | - | 4.5 | 0.5 | - | - | 190 |
| 19 | 100 | - | - | 2 | 1 | 3.5 | 1.5 | - | - | 160 |
| 20 | 100 | 30 | - | - | - | 3.2 | 2.4 | 1.44 | 0.96 | 160 |
| 21 | 100 | 30 | - | - | - | 4.8 | 0.8 | - | 2.4 | 220 |
| 22 | 100 | - | 0.5 | - | - | 7.2 | 0.8 | - | - | 300 |
| 23 | 100 | - | - | 2 | 1 | 5.6 | 2.4 | - | - | 250 |
As can be seen from Table 1, this explanation polychlorovinyl sheet material sample has thermostability preferably all more than 60 minutes the variable color time of polychlorovinyl sheet material sample in the time of 180 ± 1 ℃ that is processed to form of composite thermal stabilizer of adopting the specific embodiment of the invention.This shows that the working method of composite thermal stabilizer of the present invention and chlorine-containing polymer can be improved the stability of the course of processing of chlorine-containing polymer, and can reduce cost.
In addition, those skilled in the art also can do other variation in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention all should be included in the present invention's scope required for protection.
Claims (10)
1. composite thermal stabilizer, in mass, it comprises 10～30% ethylenediamine tetraacetic acid (EDTA), citric acid or its composition, 0～30% epoxy soybean oil, and 40～80% organo-tin het stabilizers.
2. composite thermal stabilizer as claimed in claim 1 is characterized in that: this composite thermal stabilizer comprises 10～30% the ethylenediamine tetraacetic acid (EDTA) and the mixture of citric acid.
3. composite thermal stabilizer as claimed in claim 2 is characterized in that: the content of ethylenediamine tetraacetic acid (EDTA) is 8～20%.
4. composite thermal stabilizer as claimed in claim 2 is characterized in that: the content of citric acid is 2～10%.
5. composite thermal stabilizer as claimed in claim 1 is characterized in that: the content of epoxy soybean oil is 15～30%.
6. composite thermal stabilizer as claimed in claim 1 is characterized in that: the content of organo-tin het stabilizer is 60～80%.
7. the working method of a chlorine-containing polymer, it comprises:
Mix chlorine-containing polymer and composite thermal stabilizer to form mixture, wherein in mass, this composite thermal stabilizer comprises 10～30% ethylenediamine tetraacetic acid (EDTA), citric acid or its composition, 0～30% epoxy soybean oil and 40～80% organo-tin het stabilizers; And corresponding processing aid.Heat this mixture.
8. the working method of chlorine-containing polymer as claimed in claim 7, it is characterized in that: in mass, the consumption of this composite thermal stabilizer is 4～8% of this chlorine-containing polymer.
9. the working method of chlorine-containing polymer as claimed in claim 7 is characterized in that: also should be mixed with softening agent and/or lubricant in this mixture.
10. the working method of chlorine-containing polymer as claimed in claim 9, it is characterized in that: this softening agent is a dioctyl phthalate (DOP), this lubricant comprises polyethylene wax, calcium stearate and Zinic stearas, in mass, the consumption of dioctyl phthalate (DOP) be this chlorine-containing polymer 0～65%, the consumption of polyethylene wax for this chlorine-containing polymer 0.4～1%, the calcium stearate consumption is 0～5% of this chlorine-containing polymer, and the Zinic stearas consumption is in half of calcium stearate consumption.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104277185A (en) * | 2014-09-24 | 2015-01-14 | 苏州博利迈新材料科技有限公司 | Heat-resisting anti-fogging PVC film and preparation method thereof |
| CN105647070A (en) * | 2016-04-08 | 2016-06-08 | 苏州新区华士达工程塑胶有限公司 | Flame-retardant packaging plastic film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101564960A (en) * | 2009-05-08 | 2009-10-28 | 须田凯 | Eraser manufacturing method and eraser composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101564960A (en) * | 2009-05-08 | 2009-10-28 | 须田凯 | Eraser manufacturing method and eraser composition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277185A (en) * | 2014-09-24 | 2015-01-14 | 苏州博利迈新材料科技有限公司 | Heat-resisting anti-fogging PVC film and preparation method thereof |
| CN105647070A (en) * | 2016-04-08 | 2016-06-08 | 苏州新区华士达工程塑胶有限公司 | Flame-retardant packaging plastic film |
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Effective date of registration: 20170509 Address after: Songshan Longxin Industrial Zone Longhu Road on the eastern side of the 515000 Guangdong city of Shantou Province Patentee after: GUANGDONG SHENGDA PLASTIC TECHNOLOGY CO.,LTD. Address before: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Effective date of registration: 20170509 Address after: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: Nanshan District Xili Lake of Shenzhen Polytechnic in Shenzhen, Guangdong province 518000 Patentee before: Shenzhen Polytechnic |
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Address after: 515000 Room 301, science and Technology East Road, Shantou hi tech Zone, Guangdong, 301 Patentee after: GUANGDONG SHENGDA PLASTIC TECHNOLOGY CO.,LTD. Address before: 515000 Longxin Industrial Zone, east of Songshan Road, Longhu District, Shantou, Guangdong Patentee before: GUANGDONG SHENGDA PLASTIC TECHNOLOGY CO.,LTD. |
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