CN102432961A - Composite heat stabilizer for polyvinyl chloride (PVC), and preparation method for composite heat stabilizer - Google Patents
Composite heat stabilizer for polyvinyl chloride (PVC), and preparation method for composite heat stabilizer Download PDFInfo
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- CN102432961A CN102432961A CN2011103629454A CN201110362945A CN102432961A CN 102432961 A CN102432961 A CN 102432961A CN 2011103629454 A CN2011103629454 A CN 2011103629454A CN 201110362945 A CN201110362945 A CN 201110362945A CN 102432961 A CN102432961 A CN 102432961A
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Abstract
The invention belongs to the field of chemical industry and particularly relates to a composite stabilizer for polyvinyl chloride (PVC) processing. The composite stabilizer consists of the following components in part by weight: 55 to 105 parts of main stabilizer, 0.255 to 11 parts of auxiliary stabilizer, and 10 to 35 parts of inorganic filler. The main stabilizer is a 3-dodecylthiopropionic acid metal soap stabilizer, and the chemical formula of the metal soap stabilizer is [CH3(CH2)11S(CH2)2COO]mXn, wherein X is one or more of calcium ion, zinc ion, barium ion or magnesium ion; and the metal soap stabilizer consists of 5 to 20 weight parts of metal ion and 50 to 85 parts of sulfur-containing carboxylate group. The composite stabilizer has the advantages of high thermal stability, safety and no toxicity, certain processability and lubricity and low cost.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of PVC processing with one package stabilizer and preparation method thereof.
Background technology
Thermo-stabilizer is widely used in SE industry, improves thermostability, thermotolerance and processibility in the polrvinyl chloride product course of processing.As being widely used and well behaved lead salt series of heat stablizer existing history remote at present.Wherein modal commodity are dibasic Lead Phosphite and tribasic lead sulfate.Because of its lead tolerance up to more than 80%, produce and use in contaminate environment not only, but also cause operator's lead poisoning phenomenon.This type thermal stabilizing agent is dispersed relatively poor in SE processing, also must add corresponding dispersion agent and lubricant.Though many in recent years producers coat or process mixture.But all do not solve the difficult problem that three salt and disalt lead tolerance are high, toxicity is big.Therefore developing a kind of efficient, non-toxic heat stabilizer is the purpose that common people pursue.General nontoxic or low toxicity calcium zinc stabilizer is a calcium stearate zinc series at present, mixes according to different ratios through adding other auxiliary stabilizer.Though significantly reduced the usage quantity of lead salt, still had a lot of deficiencies from aspects such as thermostability, thermotolerance, promotion plasticizing formings, and do not break away from dependence to lead salt stabilizer.
Summary of the invention
For solving PVC processing with the dependence of thermo-stabilizer to lead salt, the present invention proposes a kind of PVC with composite thermal stabilizer and preparation method thereof, it has thoroughly broken away from the dependence to lead salt, and has meliority at aspects such as thermostability, thermotolerance, promotion plasticizing formings.
Another object of the present invention provides a kind of 3-dodecyl thiohydracrylic acid metallic soap class stablizer and preparation method thereof.
Technical scheme of the present invention is: a kind of PVC uses composite thermal stabilizer, is made up of for 10～35 parts 55～105 parts of main body stablizers, 0.255～11 part of auxiliary stabilizer and mineral filler by weight.
Said main body stablizer is a 3-dodecyl thiohydracrylic acid metallic soap class stablizer, and its chemical formula is: (CH
3(CH
2)
11S (CH
2)
2COO)
mX
n, wherein X is expressed as one or more in calcium ion, zine ion, barium ion or the mg ion; It is made up of the metals ion of 5～20 weight parts and the sulfur-bearing hydroxy-acid group of 50～85 weight parts.
Said auxiliary stabilizer comprises following component by weight: 0.05～3 part of phosphite ester compound, 0.1～5 part of epoxy soybean oil, 0.005～1 part of beta-diketone compounds, 0.1～2 part of multicomponent alcoholics compound.
Wherein, said phosphite ester compound is selected from one or more the mixture in phosphorous acid hexichol one different monooctyl ester, triphenyl phosphite or the diisooctyl phenyl phosphite.Said beta-diketone compounds is mixed by hard acyl benzoyl methane and diphenylpropane-1,3-dione(DPPO), and both weight ratios are 2: 8～8: 2.Said multicomponent alcoholics compound is selected from one or more the mixture in pentaerythritol ester, ethylene glycol ethyl ethers diester or the glycerine alcohol ester.
Said mineral filler is selected from one or more the mixture in lime carbonate, permanent white or the hydrotalcite.Wherein hydrotalcite is selected magnalium carbonate type hydrotalcite for use.
PVC according to the invention adopts the preparation of physical blending method with the preparation of composite thermal stabilizer, and concrete steps are following:
At first; The 3-dodecyl thiohydracrylic acid metallic soap class stablizer of 55～105 weight parts, the beta-diketone compounds of 0.005～1 weight part and the multicomponent alcoholics compound of 0.1～2 weight part are added in the impeller; The control stirring velocity is 1200～1500r/min; When temperature rises to 50～60 ℃, add the phosphite ester compound of 0.05～3 weight part and the epoxy soybean oil of 0.1～5 weight part, be warming up to 70～75 ℃; The mineral filler that adds 10～35 weight parts, stirring 5～10min promptly gets PVC and uses composite thermal stabilizer.
Said PVC uses the composite thermal stabilizer outward appearance to be white easy mobility powder, element sulphur content>=12.0%, and free acid content≤0.15%, proportion are 1.54～1.65.
Said 3-dodecyl thiohydracrylic acid metallic soap class stablizer; In vinylformic acid is 100 weight parts, comprises the component of following weight part: 100 parts in vinylformic acid, 150～350 parts of solvents; 200～350 parts of positive Dodecyl Mercaptans; 60～80 parts of metal salt compound, 100～120 parts in alkali, 450～600 parts of deionized waters.
Wherein, said solvent is selected from one or more the mixture in n-propyl alcohol, Virahol, absolute ethyl alcohol or the propyl carbinol; Said metal salt compound is selected from one or more the mixture in calcium chloride, zinc chloride, bariumchloride or the magnesium chloride; Said alkali is selected from one or both the mixture in sodium hydroxide or the Pottasium Hydroxide.
Said 3-dodecyl thiohydracrylic acid metallic soap class stablizer chemical formula is: (CH
3(CH
2)
11S (CH
2)
2COO)
mX
n, wherein X is expressed as one or more in calcium ion, zine ion, barium ion or the mg ion.
The preparation method of said 3-dodecyl thiohydracrylic acid metallic soap class stablizer is: vinylformic acid and solvent are added in the reaction kettle, drip alkaline solution, temperature is controlled between 15～45 ℃, and the control dropping time is 1.5～2.5h; Slowly drip positive Dodecyl Mercaptan again, the control dropping time is 2～3.5h; Dropwise condensing reflux reaction 3～5h, solvent is removed in underpressure distillation; In reaction solution, add deionized water at last, slowly add metal salt compound solution then while stirring and carry out replacement(metathesis)reaction, the reaction times is 15～25min.Reaction finishes, and reaction product gets final product at 80 ℃ of following constant pressure and dries after separation, washing and dehydration.
The reaction mechanism of said preparation 3-dodecyl thiohydracrylic acid metallic soap class stablizer is following:
1, CH
2=CH
2-COOH generates CH under alkaline environment in the aprotic medium that with alcohol is the master
2=CH
2-COO
-
2, CH
2=CH
2-COO
-With-SH electrophilic addition reaction taking place, generates CH
3(CH
2)
11S-(CH
2)
2COO
-
3, CH
3(CH
2)
11S (CH
2)
2COO
-With metal salt solution generation replacement(metathesis)reaction, generate final product.
Beneficial effect of the present invention is: 1, in main body stablizer building-up process, introduce mercapto groups, improve the thermal stability in the polrvinyl chloride product course of processing greatly; 2, thoroughly broken away from dependence, reduced the problem that operator poison greatly, and have certain processibility and oilness lead salt; 3, in the preparation process, under the prerequisite that does not change thermal stability,, greatly reduce the production cost of mixture, have good economic benefits through adding mineral filler.
Embodiment
Below specify the present invention through embodiment, but the present invention is not limited to the following example, like no specified otherwise, all umbers are parts by weight.
Embodiment 1
1, prepare main body stablizer 3-dodecyl thiohydracrylic acid metallic soap class stablizer by following prescription and method:
Prescription: 100 parts in vinylformic acid, 250 parts of the mixed solvents that 1: 1 absolute ethyl alcohol of mass ratio and Virahol mix, massfraction are 160 parts of 37.5% sodium hydroxide solutions, and just Dodecyl Mercaptan is 255 parts, and massfraction is 26.74% muriate (Ca
2+/ Zn
2+Mol ratio is 2: 1) 273 parts of solution, 200 parts of deionized waters.
Preparing method: in 250 parts of adding reaction kettles of mixed solvent that 100 parts in vinylformic acid, absolute ethyl alcohol and Virahol are mixed at 1: 1; Drip massfraction and be 160 parts of 37.5% sodium hydroxide solutions, temperature is controlled between 35～40 ℃, the control dropping time is about 2h; Slowly drip 255 parts of positive Dodecyl Mercaptans again, the control dropping time is about 3h; Dropwise the about 3.5h of condensing reflux reaction, solvent is removed in underpressure distillation; In reaction solution, add 200 parts of deionized waters, slowly add massfraction then while stirring and be 26.74% muriate (Ca
2+/ Zn
2+Mol ratio is 2: 1) 273 parts of solution, carry out replacement(metathesis)reaction, the moon in reaction times is 20min.Reaction finishes, and reaction product gets 3-dodecyl thiohydracrylic acid calcium/zinc stabilizer at 80 ℃ of following constant pressure and dries after separation, washing and dehydration.
2, prepare PVC by following prescription and method and use composite thermal stabilizer:
Prescription: 70 parts of main body stablizer 3-dodecyl thiohydracrylic acid calcium/zinc stabilizers that step 1 makes; 3 parts of phosphorous acid hexichol one different monooctyl esters; 5 parts of epoxy soybean oils; 0.75 part of the beta-diketone compounds that 1: 2 hard acyl benzoyl methane of mass ratio and benzoyl methane are composited, 20 parts of 2 parts of ethylene glycol ethyl ethers diester and filler-calcium carbonates.
Preparing method: in 2 parts of adding impellers of 0.75 part of beta-diketone compounds, ethylene glycol ethyl ethers diester that 70 parts of main body stablizer 3-dodecyl thiohydracrylic acid calcium/zinc stabilizers, 1: 2 hard acyl benzoyl methane of mass ratio and benzoyl methane are composited; Control stirring velocity 1200～1500r/min; When temperature rises to 50 ℃; Add phosphorous acid hexichol one 3 parts of different monooctyl esters, 5 parts of epoxy soybean oils; Be warming up to 70 ℃, add 20 parts in mineral filler lime carbonate, stirring 5～10min discharging promptly gets PVC and uses composite thermal stabilizer.
Embodiment 2
Remove solvent replacement in the step 1 and be mixed solvent 250 that 1: 1 n-propyl alcohol of mass ratio and absolute ethyl alcohol mix especially, all the other are all identical with embodiment 1.
Embodiment 3
Be replaced by diisooctyl phenyl phosphite 3 especially except that phosphite ester compound in the step 2, all the other are all identical with embodiment 1.
Embodiment 4
Be replaced by magnalium carbonate type hydrotalcite 20 especially except that mineral filler in the step 2, all the other are all identical with embodiment 1.
Comparative Examples 1
Remove the main body stablizer be replaced by weight ratio be 1: 1 calcium stearate and Zinic stearas compound main body stablizer 70 especially, other are identical with embodiment 1.
Comparative Examples 2
Selecting weight ratio for use is 1: 14 parts of tribasic lead sulfate (three salt) and dibasic Lead Phosphite (disalt) compound stablizers.
Embodiment 1～4 is carried out performance test with Comparative Examples 1～2, and test event and method are following:
(1) static heat stability.
According to the hard slice prescription of PVC (PVC:100 part; OPE:0.4 part; Triple Pressed Stearic Acid: 0.4 part; Titanium oxide: 5 parts; Processing aid ACR:1.5 part; CPE:6 part; Stablizer (self-control sulfur-bearing one package stabilizer): 4 parts), accurately take by weighing each component, with the miniature high-speed mixing tank that mixing of materials is even; About 190 ℃ of roller temperature, plasticate on the roll spacing 1mm double roller plastic-making device in flakes, behind the following sheet; Be cut into the granular coupons of 2mm * 2mm, in the test tube of packing into, slight vibration 20 times; In glycerol bath, sample maintained (195 ± 1) ℃, the time when measuring congo-red test paper that the HCl that decomposites causes the sample top and beginning to become indigo plant, be static heat steady time.The performance test results is seen table 1.
(2) tensile strength test, elongation at break test ,-14 ℃ of low-temperature impact compression winter hardiness.
The performance test results is seen table 1.
The analysis of table 1 performance test data
Can be known that by table 1 embodiment compares with Comparative Examples, basically identical on graininess is white mobile powder; The static heat of the embodiment of the invention 1～4 all is better than Comparative Examples 1 and 2 steady time, and tensile strength also is better than Comparative Examples 1 and 2; Wherein, Comparative Examples 1 tensile strength is minimum, and embodiment 3 is the highest; Elongation at break Comparative Examples 1 is the poorest.Therefore, analysis-by-synthesis, the present invention is better than prescription used in the Comparative Examples on over-all properties.
Claims (11)
1. a PVC uses composite thermal stabilizer, it is characterized in that, is made up of for 10～35 parts 55～105 parts of main body stablizers, 0.255～11 part of auxiliary stabilizer and mineral filler by weight;
Said main body stablizer is a 3-dodecyl thiohydracrylic acid metallic soap class stablizer, and its chemical formula is: (CH
3(CH
2)
11S (CH
2)
2COO)
mX
n, wherein X is expressed as one or more in calcium ion, zine ion, barium ion or the mg ion; Said 3-dodecyl thiohydracrylic acid metallic soap class stablizer is made up of the metals ion of 5～20 weight parts and the sulfur-bearing hydroxy-acid group of 50～85 weight parts.
2. PVC according to claim 1 uses composite thermal stabilizer; It is characterized in that said auxiliary stabilizer comprises following component by weight: 0.05～3 part of phosphite ester compound, 0.1～5 part of epoxy soybean oil, 0.005～1 part of beta-diketone compounds, 0.1～2 part of multicomponent alcoholics compound.
3. PVC according to claim 2 uses composite thermal stabilizer, it is characterized in that, said phosphite ester compound is selected from one or more the mixture in phosphorous acid hexichol one different monooctyl ester, triphenyl phosphite or the diisooctyl phenyl phosphite.
4. PVC according to claim 2 uses composite thermal stabilizer, it is characterized in that, said beta-diketone compounds is mixed by hard acyl benzoyl methane and diphenylpropane-1,3-dione(DPPO), and both weight ratios are 2: 8～8: 2.
5. PVC according to claim 2 uses composite thermal stabilizer, it is characterized in that, said multicomponent alcoholics compound is selected from one or more the mixture in pentaerythritol ester, ethylene glycol ethyl ethers diester or the glycerine alcohol ester.
6. PVC according to claim 1 uses composite thermal stabilizer, it is characterized in that, said mineral filler is selected from one or more the mixture in lime carbonate, permanent white or the hydrotalcite.
7. PVC according to claim 2 uses composite thermal stabilizer; Its preparation method is: at first; The 3-dodecyl thiohydracrylic acid metallic soap class stablizer of 55～105 weight parts, the beta-diketone compounds of 0.005～1 weight part and the multicomponent alcoholics compound of 0.1～2 weight part are added in the impeller, and the control stirring velocity is 1200～1500r/min, when temperature rises to 50～60 ℃; Add the phosphite ester compound of 0.05～3 weight part and the epoxy soybean oil of 0.1～5 weight part; Be warming up to 70～75 ℃, add the mineral filler of 10～35 weight parts, stirring 5～10min promptly gets PVC and uses composite thermal stabilizer.
8. a 3-dodecyl thiohydracrylic acid metallic soap class stablizer is characterized in that, is 100 weight parts in vinylformic acid; The component that comprises following weight part: 100 parts in vinylformic acid; 150～350 parts of solvents, 200～350 parts of positive Dodecyl Mercaptans, 60～80 parts of metal salt compound; 100～120 parts in alkali, 450～600 parts of deionized waters; Said 3-dodecyl thiohydracrylic acid metallic soap class stablizer chemical formula is: (CH
3(CH
2)
11S (CH
2)
2COO)
mX
n, wherein X is expressed as one or more in calcium ion, zine ion, barium ion or the mg ion.
9. 3-dodecyl thiohydracrylic acid metallic soap class stablizer according to claim 8 is characterized in that, said solvent is selected from one or more the mixture in n-propyl alcohol, Virahol, absolute ethyl alcohol or the propyl carbinol.
10. 3-dodecyl thiohydracrylic acid metallic soap class stablizer according to claim 8 is characterized in that, said metal salt compound is selected from one or more the mixture in calcium chloride, zinc chloride, bariumchloride or the magnesium chloride; Said alkali is selected from one or both the mixture in sodium hydroxide or the Pottasium Hydroxide.
11. 3-dodecyl thiohydracrylic acid metallic soap class stablizer according to claim 8, its preparation method is: vinylformic acid and solvent are added in the reaction kettle, drip alkaline solution, temperature is controlled between 15～45 ℃, and the control dropping time is 1.5～2.5h; Slowly drip positive Dodecyl Mercaptan again, the control dropping time is 2～3.5h; Dropwise condensing reflux reaction 3～5h, solvent is removed in underpressure distillation; In reaction solution, add deionized water at last, slowly add metal salt compound solution then while stirring and carry out replacement(metathesis)reaction, the reaction times is 15～25min.Reaction finishes, and reaction product gets final product at 80 ℃ of following constant pressure and dries after separation, washing and dehydration.
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Cited By (10)
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| CN103387720A (en) * | 2012-05-10 | 2013-11-13 | 荣升塑胶（上海）有限公司 | Wallpaper film |
| CN103387719A (en) * | 2012-05-10 | 2013-11-13 | 荣升塑胶（上海）有限公司 | Polyvinyl chloride (PVC) embossed film for using on gypsum board and manufacturing method of PVC embossed film |
| CN104672649A (en) * | 2013-11-26 | 2015-06-03 | 徐小玲 | A liquid plastic formula |
| CN105431483A (en) * | 2013-06-24 | 2016-03-23 | 倍耐力轮胎股份公司 | Tyre for vehicle wheels |
| CN106479015A (en) * | 2015-08-27 | 2017-03-08 | 奕益实业有限公司 | Modified polymeric materials and composite stabilizer compositions |
| CN106478983A (en) * | 2015-09-01 | 2017-03-08 | 奕益实业有限公司 | Combined type tranquilizer constituent and modified polymeric material |
| CN107474557A (en) * | 2017-09-06 | 2017-12-15 | 戴琪 | A kind of preparation method of environment-benign heat stabilizer |
| CN109467843A (en) * | 2018-10-30 | 2019-03-15 | 东莞常平金业电器制品有限公司 | A kind of PVC micelle and preparation method thereof for manufacturing medical electric wire |
| CN112724558A (en) * | 2020-12-30 | 2021-04-30 | 杭州朝盛塑业有限公司 | Composite PVC heat stabilizer and preparation method thereof |
| CN112852067A (en) * | 2021-01-06 | 2021-05-28 | 江苏联盟化学有限公司 | Flaky calcium-zinc PVC heat stabilizer and preparation method thereof |
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| CN103387720A (en) * | 2012-05-10 | 2013-11-13 | 荣升塑胶（上海）有限公司 | Wallpaper film |
| CN103387719A (en) * | 2012-05-10 | 2013-11-13 | 荣升塑胶（上海）有限公司 | Polyvinyl chloride (PVC) embossed film for using on gypsum board and manufacturing method of PVC embossed film |
| CN105431483A (en) * | 2013-06-24 | 2016-03-23 | 倍耐力轮胎股份公司 | Tyre for vehicle wheels |
| CN105431483B (en) * | 2013-06-24 | 2017-10-10 | 倍耐力轮胎股份公司 | Tire for wheel |
| CN104672649A (en) * | 2013-11-26 | 2015-06-03 | 徐小玲 | A liquid plastic formula |
| CN106479041A (en) * | 2015-08-27 | 2017-03-08 | 奕益实业有限公司 | Modified polymeric materials and composite stabilizer compositions |
| CN106479015A (en) * | 2015-08-27 | 2017-03-08 | 奕益实业有限公司 | Modified polymeric materials and composite stabilizer compositions |
| CN106479041B (en) * | 2015-08-27 | 2019-04-26 | 奕益实业有限公司 | Modified polymeric materials and composite stabilizer compositions |
| CN106478983A (en) * | 2015-09-01 | 2017-03-08 | 奕益实业有限公司 | Combined type tranquilizer constituent and modified polymeric material |
| CN106479040A (en) * | 2015-09-01 | 2017-03-08 | 奕益实业有限公司 | Combined type tranquilizer constituent and modified polymeric material |
| CN107474557A (en) * | 2017-09-06 | 2017-12-15 | 戴琪 | A kind of preparation method of environment-benign heat stabilizer |
| CN109467843A (en) * | 2018-10-30 | 2019-03-15 | 东莞常平金业电器制品有限公司 | A kind of PVC micelle and preparation method thereof for manufacturing medical electric wire |
| CN109467843B (en) * | 2018-10-30 | 2021-01-22 | 东莞常平金业电器制品有限公司 | PVC colloidal particle for manufacturing medical electric wire and preparation method thereof |
| CN112724558A (en) * | 2020-12-30 | 2021-04-30 | 杭州朝盛塑业有限公司 | Composite PVC heat stabilizer and preparation method thereof |
| CN112852067A (en) * | 2021-01-06 | 2021-05-28 | 江苏联盟化学有限公司 | Flaky calcium-zinc PVC heat stabilizer and preparation method thereof |
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