CN102432961B - 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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- CN102432961B CN102432961B CN201110362945.4A CN201110362945A CN102432961B CN 102432961 B CN102432961 B CN 102432961B CN 201110362945 A CN201110362945 A CN 201110362945A CN 102432961 B CN102432961 B CN 102432961B
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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 one package stabilizer and preparation method thereof.
Background technology
Thermo-stabilizer is widely used in PVC industry, improves thermostability, thermotolerance and processibility in the polrvinyl chloride product course of processing.As being widely used at present and well behaved lead salt series of heat stablizer, existing history remote.Wherein modal commodity are dibasic Lead Phosphite and tribasic lead sulfate.Because its lead tolerance is up to more than 80%, produce and use procedure in contaminate environment not only, but also cause operator's lead poisoning phenomenon.This type thermal stabilizing agent is dispersed poor in polyvinyl chloride processing, also must add corresponding dispersion agent and lubricant.Although many producers are coated or make mixture in recent years.But all do not solve three salt and disalt lead tolerance is high, toxicity is a large difficult problem.Therefore developing a kind of efficient, non-toxic heat stabilizer is the object that common people pursue.General nontoxic or low toxicity calcium zinc stabilizer is calcium stearate zinc series at present, by adding other auxiliary stabilizer to mix according to different ratios.Although greatly 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 the dependence to lead salt stabilizer.
Summary of the invention
For solving PVC processing dependence to lead salt with thermo-stabilizer, the present invention proposes composite thermal stabilizer and preparation method thereof for a kind of PVC, it has thoroughly broken away from the dependence to lead salt, and has superiority at aspects such as thermostability, thermotolerance, promotion plasticizing formings.
Another object of the present invention is to provide a kind of 3-dodecyl thiohydracrylic acid metal soap stablizer and preparation method thereof.
Technical scheme of the present invention is: a kind of PVC composite thermal stabilizer, is comprised of 10～35 parts of 55～105 parts of Soil stability agent, 0.255～11 part of auxiliary stabilizer and mineral fillers by weight.
Described Soil stability agent is 3-dodecyl thiohydracrylic acid metal soap 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 magnesium ion; The sulfur-bearing hydroxy-acid group of its metal ion by 5～20 weight parts and 50～85 weight parts forms.
Described 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, described phosphite ester compound is selected from one or more the mixture in the different monooctyl ester of phosphorous acid hexichol one, triphenyl phosphite or diisooctyl phenyl phosphite.Described 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.Described multicomponent alcoholics compound is selected from one or more the mixture in pentaerythritol ester, ethylene glycol ethyl ethers diester or glycerine alcohol ester.
Described mineral filler is selected from one or more the mixture in calcium carbonate, barium sulfate or hydrotalcite.Wherein hydrotalcite is selected magnalium carbonate type hydrotalcite.
PVC of the present invention adopts the preparation of physical blending method with the preparation of composite thermal stabilizer, and concrete steps are as follows:
First, 3-dodecyl thiohydracrylic acid metal soap stablizer, the beta-diketone compounds of 0.005～1 weight part and the multicomponent alcoholics compound of 0.1～2 weight part of 55～105 weight parts are added in homogenizer, 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, stirs 5～10min and obtains PVC composite thermal stabilizer.
Described PVC is white easy mobility powder by composite thermal stabilizer outward appearance, element sulphur content >=12.0%, and free acid content≤0.15%, proportion is 1.54～1.65.
Described 3-dodecyl thiohydracrylic acid metal soap stablizer, take vinylformic acid as 100 weight parts, the component that comprises following weight part: 100 parts, vinylformic acid, 150～350 parts of solvents, 200～350 parts of positive Dodecyl Mercaptans, 60～80 parts of metal salt compound, 100～120 parts, alkali, 450～600 parts of deionized waters.
Wherein, described solvent is selected from one or more the mixture in n-propyl alcohol, Virahol, dehydrated alcohol or propyl carbinol; Described metal salt compound is selected from one or more the mixture in calcium chloride, zinc chloride, bariumchloride or magnesium chloride; Described alkali is selected from one or both the mixture in sodium hydroxide or potassium hydroxide.
Described 3-dodecyl thiohydracrylic acid metal soap 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 magnesium ion.
The preparation method of described 3-dodecyl thiohydracrylic acid metal soap stablizer is: vinylformic acid and solvent are added in reactor, drip alkaline solution, temperature is controlled between 15～45 ℃, and control time for adding is 1.5～2.5h; Slowly drip positive Dodecyl Mercaptan, control time for adding is 2～3.5h again; Dropwise condensing reflux reaction 3～5h, solvent is removed in underpressure distillation; In the most backward reaction solution, add deionized water, then slowly add while stirring metal salt compound solution to carry out replacement(metathesis)reaction, the reaction times is 15～25min.React complete, reaction product through separated, wash and dewater after, constant pressure and dry at 80 ℃.
The reaction mechanism of described preparation 3-dodecyl thiohydracrylic acid metal soap stablizer is as follows:
1, CH
2=CH
2-COOH, take alcohol in main aprotic medium, generates CH under alkaline environment
2=CH
2-COO
-;
2, CH
2=CH
2-COO
-there is electrophilic addition reaction with-SH, generate 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 Soil stability agent building-up process, introduce mercapto groups, greatly improve the thermal stability in the polrvinyl chloride product course of processing; 2, thoroughly break away from the dependence to lead salt, greatly reduced the poisoning problem of operator, and there is certain processibility and oilness; 3, in preparation process, do not changing under the prerequisite of thermal stability, by adding mineral filler, greatly reducing the production cost of mixture, thering is good economic benefit.
Embodiment
Illustrate by the following examples the present invention, but the present invention is not limited to the following example, if no special instructions, all umbers are parts by weight.
Embodiment 1
1, by following formula and method, prepare Soil stability agent 3-dodecyl thiohydracrylic acid metal soap stablizer:
Formula: 100 parts, vinylformic acid, 250 parts of the mixed solvents that the mass ratio dehydrated alcohol of 1: 1 and Virahol mix, 160 parts of the sodium hydroxide solutions that massfraction is 37.5%, 255 parts of positive Dodecyl Mercaptans, the muriate (Ca that massfraction is 26.74%
2+/ Zn
2+mol ratio is 2: 1) 273 parts of solution, 200 parts of deionized waters.
Preparation method: 250 parts of mixed solvents that 100 parts, vinylformic acid, dehydrated alcohol and Virahol are mixed at 1: 1 add in reactor, 160 parts of the sodium hydroxide solutions that dropping massfraction is 37.5%, temperature is controlled between 35～40 ℃, control time for adding is about 2h; Slowly drip again 255 parts of positive Dodecyl Mercaptans, control time for adding and be about 3h; Dropwise condensing reflux and react about 3.5h, solvent is removed in underpressure distillation; In reaction solution, add 200 parts of deionized waters, then slowly adding while stirring massfraction is 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.React complete, reaction product through separated, wash and dewater after, at 80 ℃, constant pressure and dry obtains 3-dodecyl thiohydracrylic acid calcium/zinc stabilizer.
2, by following formula and method, prepare PVC composite thermal stabilizer:
Formula: 70 parts of Soil stability agent 3-dodecyl thiohydracrylic acid calcium/zinc stabilizers that step 1 makes, 3 parts of the different monooctyl esters of phosphorous acid hexichol one, 5 parts of epoxy soybean oils, 0.75 part of the beta-diketone compounds that the mass ratio hard acyl benzoyl methane of 1: 2 and benzoyl methane are composited, 20 parts of 2 parts of ethylene glycol ethyl ethers diester and filler-calcium carbonates.
Preparation method: 2 parts of 0.75 part of beta-diketone compounds, ethylene glycol ethyl ethers diester that 70 parts of Soil stability agent 3-dodecyl thiohydracrylic acid calcium/zinc stabilizers, the mass ratio hard acyl benzoyl methane of 1: 2 and benzoyl methane are composited add in homogenizer, control stirring velocity 1200～1500r/min, when temperature rises to 50 ℃, add 3 parts of the different monooctyl esters of phosphorous acid hexichol one, 5 parts of epoxy soybean oils, be warming up to 70 ℃, add 20 parts, mineral filler calcium carbonate, stir 5～10min discharging and obtain PVC composite thermal stabilizer.
Embodiment 2
Except solvent replacement in step 1 be the mixed solvent 250 that mixes of the mass ratio n-propyl alcohol of 1: 1 and dehydrated alcohol especially, all the other are all identical with embodiment 1.
Embodiment 3
Except phosphite ester compound in step 2 is replaced by diisooctyl phenyl phosphite 3 especially, all the other are all identical with embodiment 1.
Embodiment 4
Except mineral filler in step 2 is replaced by magnalium carbonate type hydrotalcite 20 especially, all the other are all identical with embodiment 1.
Comparative example 1
Except Soil stability agent be replaced by weight ratio be the compound Soil stability agent 70 of the calcium stearate of 1: 1 and Zinic stearas especially, other are identical with embodiment 1.
Comparative example 2
Selecting weight ratio is 4 parts of the compound stablizers of tribasic lead sulfate (three salt) and the dibasic Lead Phosphite (disalt) of 1: 1.
Embodiment 1～4 and comparative example 1～2 are carried out to performance test, and test event and method are as follows:
(1) static heat stability.
According to the hard slice prescription of PVC (PVC:100 part; OPE:0.4 part; Stearic acid: 0.4 part; Titanium dioxide: 5 parts; Processing aid ACR:1.5 part; CPE:6 part; Stablizer (self-control sulfur-bearing one package stabilizer): 4 parts), accurately take each component, with miniature high-speed mixing tank, mixing of materials is even, in 190 ℃ of left and right of roller temperature, on roll spacing 1mm double roller plastic-making device, plasticate in flakes, after lower, be cut into the granular coupons of 2mm * 2mm, pack in test tube, slight vibration 20 times, in glycerol bath, sample is maintained (195 ± 1) ℃, the time when measuring congo-red test paper that the HCl decomposite causes sample top and starting to become indigo plant, be static heat steady time.The performance test results is in Table 1.
(2) tensile strength test, elongation at break test ,-14 ℃ of low-temperature impact compression winter hardiness.
The performance test results is in Table 1.
The analysis of table 1 performance test data
As shown in Table 1, embodiment compares with comparative example, basically identical on graininess, is white mobility powder; The static heat of the embodiment of the present invention 1～4 is all better than comparative example 1 and 2 steady time, and tensile strength is also better than comparative example 1 and 2; Wherein, comparative example 1 tensile strength is minimum, and embodiment 3 is the highest; Elongation at break comparative example 1 is the poorest.Therefore, comprehensively analyze, the present invention is better than formula used in comparative example on over-all properties.
Claims (1)
1. a PVC composite thermal stabilizer, is characterized in that, by following formula and method, prepares Soil stability agent 3-dodecyl thiohydracrylic acid metal soap stablizer:
Formula: 100 parts, vinylformic acid, 250 parts of the mixed solvents that the dehydrated alcohol of mass ratio 1:1 and Virahol mix, 160 parts of the sodium hydroxide solutions that massfraction is 37.5%, 255 parts of positive Dodecyl Mercaptans, massfraction is 273 parts of 26.74% chloride solns, chloride soln Ca
2+/ Zn
2+mol ratio is 2:1,200 parts of deionized waters;
Preparation method: 250 parts of mixed solvents that 100 parts, vinylformic acid, dehydrated alcohol and Virahol 1:1 are mixed add in reactor, 160 parts of the sodium hydroxide solutions that dropping massfraction is 37.5%, temperature is controlled between 35～40 ℃, control time for adding is 2h; Slowly drip 255 parts of positive Dodecyl Mercaptans, control time for adding is 3h again; Dropwise condensing reflux reaction 3.5h, solvent is removed in underpressure distillation; In reaction solution, add 200 parts of deionized waters, then slowly adding while stirring massfraction is 273 parts of 26.74% chloride solns, chloride soln Ca
2+/ Zn
2+mol ratio is 2:1, carries out replacement(metathesis)reaction, and the reaction times is 20min; React complete, reaction product through separated, wash and dewater after, at 80 ℃, constant pressure and dry obtains 3-dodecyl thiohydracrylic acid calcium/zinc stabilizer;
By following formula and method, prepare PVC composite thermal stabilizer:
Formula: 70 parts of Soil stability agent 3-dodecyl thiohydracrylic acid calcium/zinc stabilizers that step 1 makes, 3 parts of the different monooctyl esters of phosphorous acid hexichol one, 5 parts of epoxy soybean oils, 0.75 part of the hard acyl benzoyl methane of mass ratio 1:2 and the beta-diketone compounds that benzoyl methane is composited, 20 parts of 2 parts of ethylene glycol ethyl ethers diester and filler-calcium carbonates;
Preparation method: 2 parts of the hard acyl benzoyl methane of 70 parts of Soil stability agent 3-dodecyl thiohydracrylic acid calcium/zinc stabilizers, mass ratio 1:2 and 0.75 part of beta-diketone compounds, ethylene glycol ethyl ethers diester that benzoyl methane is composited are added in homogenizer, control stirring velocity 1200～1500r/min, when temperature rises to 50 ℃, add 3 parts of the different monooctyl esters of phosphorous acid hexichol one, 5 parts of epoxy soybean oils, be warming up to 70 ℃, add 20 parts, mineral filler calcium carbonate, stir 5～10min discharging and obtain PVC composite thermal stabilizer.
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| 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 |
| CN103387720A (en) * | 2012-05-10 | 2013-11-13 | 荣升塑胶（上海）有限公司 | Wallpaper film |
| ITMI20131048A1 (en) * | 2013-06-24 | 2014-12-25 | Pirelli | TIRE FOR VEHICLE WHEELS |
| CN104672649A (en) * | 2013-11-26 | 2015-06-03 | 徐小玲 | A liquid plastic formula |
| 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 |
| CN107474557A (en) * | 2017-09-06 | 2017-12-15 | 戴琪 | A kind of preparation method of environment-benign heat stabilizer |
| 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 |
| CN112724558B (en) * | 2020-12-30 | 2022-08-05 | 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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| DE10301675A1 (en) * | 2003-01-17 | 2004-07-29 | Crompton Vinyl Additives Gmbh | Stabilizer mixtures for chloropolymer, e.g. PVC, e.g. for flooring, vehicle part, foil, pipe, molding, wire covering or profile, contain alkanolamine or reaction product with epoxide and amino(thio)uracil or cyanoacetyl(thio)urea |
| CN101602863B (en) * | 2009-06-22 | 2011-09-14 | 温州天盛塑料助剂有限公司 | Environmental-friendly dust-free calcium-zinc composite heat stabilizer for PVC processing |
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