CN101747529B - Ca-Zn liquid composite stabilizing agent and application thereof - Google Patents
Ca-Zn liquid composite stabilizing agent and application thereof Download PDFInfo
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- CN101747529B CN101747529B CN2009101550756A CN200910155075A CN101747529B CN 101747529 B CN101747529 B CN 101747529B CN 2009101550756 A CN2009101550756 A CN 2009101550756A CN 200910155075 A CN200910155075 A CN 200910155075A CN 101747529 B CN101747529 B CN 101747529B
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Abstract
The invention relates to a PVC heat stabilizing agent, in particular to a liquid composite stabilizing agent used by PVC tubing and pipe fitting and application thereof. Ca-Zn liquid composite stabilizing agent is composed of the following components in percentage by weight: 25-40% of calcium carboxylate containing 8-12 wt% of excess alkali, 5-20% of zinc carboxylate containing 10-20 wt% of zinc, 10-30% of phosphite ester, 5-30% of epoxidized soybean oil, 2-8% of beta-diketone, 1-8% of antioxygen, 5-10% of polyol ester and 10-20% of solvent. The invention adopts a proper quantity of metal stabilizer and synergetic stabilizing agent to cooperate, has reasonable prescription and simple method, keeps favourable heat stability and transparency to PVC products, conforms to environmental protection requirements, has the characteristics of favourable performance, low production cost and the like and is suitable for popularizing and applying.
Description
Technical field
The present invention relates to a kind of PVC thermo-stabilizer, relate in particular to a kind of pvc pipe material, pipe fitting liquid composite stabilizing agent and application thereof.
Background technology
The lead salt thermo-stabilizer is disabled in the U.S. and European Union at present, has replaced the lead salt thermo-stabilizer at U.S.'s organo-tin het stabilizer comprehensively, and Europe is then based on calcium/zinc heat stabilizer.In the Asia, because production cost and technical elements, the nations of China and India is still the user of lead salt one package stabilizer maximum.In China, along with the raising of national life level, people are perfect gradually to the growing interest of health problem and corresponding environmental regulation, the lead salt one package stabilizer will be by security higher and cost reasonably, the kind of compliance with environmental protection requirements replaces.Increasingly stringent has also proposed stern challenge to our thermo-stabilizer industry after especially plumbous declaration is prohibited in June, 2009 pipeline special commission issue.Therefore, all stricter requirement is proposed for the environmental protection and the safe handling of tubing, pipe fitting product no matter be home consumption or products export.This is from Chinese chemical industry newspaper report on July 24th, 2009: June 16, China plastic conduit Professional Committee of plastic working TIA is in annual meeting in 2009, having passed through feeds water forbids using the declaration of lead salt thermo-stabilizer with polyvinyl chloride pipeline, indicate that China completely forbids the beginning of using the lead salt thermo-stabilizer in this field.And the issue of this distance former Ministry of Construction on March 18th, 2004 is over and done with more than 5 years about recommend to use the bulletin of non-lead salt thermo-stabilizer in same field.Developed country such as the U.S., Japan has not just used the lead salt thermo-stabilizer as far back as the sixties in last century; The timetable that also has been ranked on the lead salt thermo-stabilizer problem is being used in Europe: forbidding was forbidden the use of forbidding the lead salt thermo-stabilizer in 75%, 2015 year 100% in 25%, 2010 year in 2005.4 family's tissues such as the plastics association in Europe, plastic door-window association, pipe part association, metope association propose the self-discipline pact, require each member enterprise to stop the use of lead salt thermo-stabilizer fully in 2015.Sweden, Holland have forbidden in 2002 that the lead salt thermo-stabilizer is used for drinking water pipeline.Britain forbids that in December, 2003 the lead salt thermo-stabilizer is used for drinking water pipeline.
Follow the plumbous trend of taboo in the world closely, from 2003, China also began to pay close attention to lead salt thermo-stabilizer problem.According to the director Song Shuyan of pipe-line equipment portion of the water supply and drainage association introduction of Chinese cities and towns, tap water once took place and enters and found the lead incident that exceeds standard behind the floor in Beijing, was exactly that pipeline excess inferior is used due to the lead salt thermo-stabilizer.For filling out urbanite water consumption safety in the guarantee city, Beijing and Shanghai City take the lead in having passed through prohibiting plumbous decision in water service pipe.The bulletin of " apply and restriction bans use of technology " of former Ministry of Construction issue in 2004 spells out, and feedwater must be used non-lead salt thermo-stabilizer with polyvinyl chloride pipe.Through effort in 5 years, up to the present, the enterprise of polyvinyl chloride pipeline manufacturing enterprise, the especially standard of China's overwhelming majority brought into use the thermo-stabilizer of non-lead salts.The enterprise that has uses organo-tin het stabilizer, the enterprise that also has calcium zinc or rare earth complex class thermo-stabilizer.Polychloroethylene heat stabilizer just towards low toxicity, nontoxic, pollution-free, compound, direction develops efficiently.
Now equal both at home and abroad emphasis development and application non-toxic stabilizer, organotin is as one of thermo-stabilizer main and outstanding in the PVC processing non-toxic heat stabilizer, application in outlet and domestic high-end profiled material, tubing, pipe fitting are processed in a large number at present, be mainly kinds such as methyl tin and butyl tin, this also is the major impetus that domestic in recent years organotin output increases fast.The organic tin stablizer is one of best thermo-stabilizer of polyvinyl chloride (PVC).The research of organo-tin het stabilizer, existing nearly 60 years history.Abroad, the development of organic tin stablizer is very fast, especially more outstanding with the U.S..The organo-tin compound that can be used as the use of PVC thermo-stabilizer has several thousand kinds at least, but extensively obtains the kind of industry and commodity achievement, and its basic structure is no more than 20 kinds.Organotin has thermostability as the PVC thermo-stabilizer and weathering resistance is good, prevent excellent properties such as initial coloring is good, nothing (low) is malicious, transparent, at the high packing articles of hygienic requirements such as food, medicine, hard, semi-rigid clear sheet, sheet material, soft transparent PVC film, the food grade bottle, in the use of upper hose material etc., it has occupied irreplaceable status.Current, each state all thermo-stabilizers such as development high effect nontoxic, multi-functional, non-heavy metalization, polymer quantification, Compositional type, low costs as basic orientation.Stablizer with other type is compared, the stablizer in the more approaching ideal of the over-all properties of organic tin stablizer.But all organic tin stablizers, tubular construction is not how, and main drawback is that manufacturing cost is more much higher than Pb stabilizer or metallic soap class mixture.And PVC plastics factory is when using, in the mixing process, the evaporation rate of organotin stabilizer will be accelerated, have the organotin volatile matter of some amount this moment, a small amount of organotin and PVC reaction product one organotin prussiate may also can mix. and together emit together with dust, water vapor, make original just bad more because of the environment of the abominable batch mixing workshop section of dust pollution labor condition.Adopt traditional hand-fed, the mixing method of execute-in-place because present most of factories more, rather than the level of automation height, manually participate in few whole mixing material system, so the workman of this workshop section is very easily by dust and toxic gas infringement; In the opposing party's surface and PVC machine-shaping process. at high temperature PVC will decompose. unstable atom in organotin stabilizer and the PVC molecule forms ligand. and in ligand carboxylic acid ester groups and the unsettled chlorine atomic substitutions of organotin. make PVC keep stablizing, produce the organotin muriate simultaneously.The toxicity of this compound is higher than organotin stabilizer itself far away.These organotin muriates at high temperature also can evaporate. bring harm to the site operation personnel.
Organotin is inadequate under China's actual conditions aspect alternative lead salt, because most plastics enterprise adopts traditional lead salt formula system, the PVC-U boardy product of being produced also mostly is white greatly.If be directly changed into the thiol organotin formula system, not only to the surperficial erosion resistance and the coating of screw rod, barrel and crusher have relatively high expectations (also should change sometimes) comprehensively, and because thiol organotin and plumbous sulfide staining, certain link is careless slightly in the processing will cause crossed contamination, it is color patterned to cause tube surfaces ash to occur, and uses after the product fragmentation after polluting and also can bring secondary pollution.Secondly, it is more different that the formulating of recipe of organotin system, technology controlling and process and lead are that formula system has, and decomposition rate is very fast.And the component of other sulfur-bearing such as filler, tinting material react the phenomenon that causes look in plumbous, cadmium stabilizer and prescription.In the polyvinyl chloride prescription of leaded, cadmium stabilizer, add some material later that contain the tin mercaptides used as stabilizers and also this fraud can take place.But change many reasons such as crossed contamination of bringing after the organotin stabilizer system, numerous tubing, pipe fitting enterprise are hung back.Calcium zinc stabilising system is then different, and it is quite similar with prescription, lubrication mechanism and the complete processing of lead salt formula system, is come to follow a well mapped-out plan convenient control by the lead salt conversion.And Ca-Zn composite heat stabilizer is the kind that wherein has most development prospect, calcium zinc heat stabilizer commonly used is nontoxic, cheap, oilness is good, and with the lead salt formula system quite similar aspect prescription, lubrication mechanism and the complete processing, substitute the lead salt stabilizer ratio and be easier to.But zinc soap often causes goods " zinc burning ", thereby thermal stability is relatively poor, and work range is narrow.In the occasion that product properties is had relatively high expectations, the application of zinc soap and zinc-base composite prod has been subjected to certain restriction.
The applicant has applied for that on 06 26th, 2007 the prescription of this patent thermo-stabilizer of a kind of double matching type heat stabilizer (patent No. is 200710069728.X) is: in parts by weight, the organic liquid single component material 5～20 of the organic liquid single component material 40～60 of calcium metal, the organic liquid single component material 5～20 of zinc metal, magnesium metal, the organic liquid single component material 15～40 of barium metal, organic stabilizer 5～20, Synergistic stabilizer 5～8; Wherein said organic stabilizer is diphenyl thiourea or stearyl benzene alkane, described Synergistic stabilizer is the phosphorous acid esters materials, has reasonable recipe, method is easy, to PVC goods Heat stability is good, characteristics such as excellent property, production cost are low are suitable for and apply.
Summary of the invention
Technological deficiency for plumbous thermo-stabilizer of the PVC that solves existing domestic use and organo-tin het stabilizer existence, an object of the present invention is to provide a kind of Ca-Zn liquid composite stabilizing agent, this one package stabilizer can satisfy the tubing that the different levels of consumption require, the complete processing of pipe fitting (present domestic PVC pipe, the mass discrepancy of pipe fitting is very big, be mainly reflected in the stopping composition addition and add about 10 parts to 100 parts PVC interpolations more than 100 parts from 100 parts of PVC, this to the test of lead salt substitute products greatly, also be the substitute products one of the main reasons that is difficult to apply up to now), good to PVC goods thermal stability, have leadless environment-friendly, the characteristics that production cost is low.Another one purpose of the present invention provides pvc pipe material and the pipe fitting that uses above-mentioned one package stabilizer.
In order to realize first above-mentioned technical purpose, the present invention has adopted following technical scheme:
Ca-Zn liquid composite stabilizing agent, this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic 25%～40% of crossing alkali of calcium weight metal degree 8%～12%
Acid calcium
The zinc carboxylate 5%～20% of zinc weight metal degree 10%～20%
Phosphorous acid ester 10%～30%
Epoxy soybean oil 5%～30%
Beta-diketone compound 2%～8%
Oxidation inhibitor 1%～8%
Polyol ester 5%～10%
Solvent 10%～20%
The total amount of above-mentioned each component is 100%.
As preferably, this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic 28%～38% of crossing alkali of calcium weight metal degree 8%～12%
Acid calcium
The zinc carboxylate 8%～18% of zinc weight metal degree 10%～20%
Phosphorous acid ester 12%～28%
Epoxy soybean oil 8%～28%
Beta-diketone compound 3%～8%
Oxidation inhibitor 2%～8%
Polyol ester 5%～10%
Solvent 12%～20%
The total amount of above-mentioned each component is 100%.
As preferred again, this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic 30%～35% of crossing alkali of calcium weight metal degree 8%～12%
Acid calcium
The zinc carboxylate 10%～15% of zinc weight metal degree 10%～20%
Phosphorous acid ester 15%～25%
Epoxy soybean oil 10%～25%
Beta-diketone compound 5%～8%
Oxidation inhibitor 3%～8%
Polyol ester 5%～10%
Solvent 15%～20%
The total amount of above-mentioned each component is 100%.
As preferably, above-mentioned phosphorous acid ester is selected Phenyl Di-2-ethyl Hexyl Phosphite, bis-phosphite, three nonyl phenyl phosphites, triisodecyl phosphite ester, phosphorous acid phenyl two isodecyl esters, phenylbenzene isodecyl phosphorous acid ester, the different monooctyl ester of phosphorous acid phenylbenzene, triphenyl phosphite, tetraphenyl dipropylene glycol diphosphites, tricresyl phosphite bay alcohol ester, three (dipropylene glycol) phosphorous acid ester, phenylbenzene phosphorous acid ester, poly-4 for use, 4, isopropylidene diphenol C
12-15One or both mixing in the alcohol phosphorous acid ester.
As preferably, above-mentioned beta-diketone compound is selected one or both mixing in diphenylpropane-1,3-dione(DPPO) and the stearyl formyl methane for use.
As preferably, above-mentioned oxidation inhibitor is selected one or more in antioxidant 1076, antioxidant 1010 and the dihydroxyphenyl propane for use.
As preferably, above-mentioned polyol ester is selected the carboxylate of tetramethylolmethane, Dipentaerythritol, TriMethylolPropane(TMP) or Sorbitol Powder for use.
As preferably, above-mentioned solvent is selected diethylene glycol dimethyl ether or high-boiling point kerosene for use.The present invention adopts diethylene glycol dimethyl ether or high-boiling point kerosene to improve the flowability of thermo-stabilizer.
The present invention adopts the zinc metal and the calcium metal is composite is as its reason of main stabilizer: be 1～5min the action time of zinc metal, and action time is short, rapid-action, has good initial coloration, but " zinc burning " phenomenon that exists.The calcium metal is the effect that always exists from start to end, and long action time, onset are slow; But the calcium metal lacks the ability that stops the polyenoid chain to be grown up, and can not suppress initial coloration, and initial coloring is serious.The quality of zinc carboxylate 5%～20% can satisfy rapid-action, and has good initial coloration, and the quality of crossing the liquid carboxylic calcium 25%～40% of alkali can satisfy long effect.
In addition, the present invention has also added Synergistic stabilizer, as phosphorous acid ester, epoxy soybean oil, beta-diketone compound and polyol ester, Synergistic stabilizer can effectively stop owing to add zinc metal generation " zinc burning " phenomenon, Synergistic stabilizer can adsorb the HCl of generation simultaneously, use as stablizer, can overcome because the time difference that the composite back of zinc metal and calcium metal exists.The present invention adopts the Synergistic stabilizer of zinc metal and the composite adding of calcium metal amount of the present invention, can produce maximum synergy, thereby obtains the satisfactory stability effect.
In order to realize second above-mentioned technical purpose, the present invention has adopted following technical scheme:
A kind of pvc pipe material, this pvc pipe spare have added the described Ca-Zn liquid composite stabilizing agent of above-mentioned any one technical scheme of 1%～2% weight percent.
A kind of pvc pipe spare, this pvc pipe material have added the described Ca-Zn liquid composite stabilizing agent of above-mentioned any one technical scheme of 2%～3% weight percent.
The present invention is owing to adopted above-mentioned technical scheme, adopted the mating reaction of the metal(lic)stabilizer and the Synergistic stabilizer of sufficient quantity, reasonable recipe, method are easy, can keep good thermal stability, the transparency can meet environmental protection requirement again to the PVC goods, characteristics such as excellent property, production cost are low are suitable for and apply.Certainly, product of the present invention should not limit and only be used for pvc pipe material, pipe fitting, and other PVC products are also had effectively effect on thermal.
Description of drawings
Fig. 1 is applied to the flow curve figure of upper hose material for thermo-stabilizer, and O is an organotin stabilizer, and Δ is the embodiment of the invention 1 a described one package stabilizer.
Fig. 2 is applied to the flow curve figure of upper hose spare for thermo-stabilizer, and O is an organotin stabilizer, and Δ is the embodiment of the invention 1 a described one package stabilizer.
The upper hose spare extruding test photo figure that Fig. 3 does for embodiment 1 described product.
Embodiment
Below the specific embodiment of the present invention and beneficial effect are made a detailed explanation.
Embodiment 1
Ca-Zn liquid composite stabilizing agent, this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic calcium 35% of crossing alkali of calcium weight metal degree 10%
The zinc carboxylate 10% of zinc weight metal degree 15%
Phenyl Di-2-ethyl Hexyl Phosphite 20%
Epoxy soybean oil 7.5%
Diphenylpropane-1,3-dione(DPPO) 4.0%
Antioxidant 1076 2.5%
Pentaerythritol ester 6.0%
Diethylene glycol dimethyl ether 15%.
Each above-mentioned component ingredient mixing and stirring is prepared described Ca-Zn liquid composite stabilizing agent.
Embodiment 2
Ca-Zn liquid composite stabilizing agent, this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic calcium 30% of crossing alkali of calcium weight metal degree 10%
The zinc carboxylate 15% of zinc weight metal degree 15%
Bis-phosphite 15%
Epoxy soybean oil 16%
Stearyl formyl methane 5.5%
Antioxidant 1076 1.5%
Pentaerythritol ester 8.0%
Diethylene glycol dimethyl ether 10%.
Each above-mentioned component ingredient mixing and stirring is prepared described Ca-Zn liquid composite stabilizing agent.
Embodiment 3
Ca-Zn liquid composite stabilizing agent, this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic calcium 20% of crossing alkali of calcium weight metal degree 10%
The zinc carboxylate 12% of zinc weight metal degree 15%
Bis-phosphite 8.0%
Phenylbenzene isodecyl phosphorous acid ester 10.0%
Epoxy soybean oil 15%
Stearyl formyl methane 3.5%
Diphenylpropane-1,3-dione(DPPO) 3.5%
Dihydroxyphenyl propane 4.5%
Dipentaerythritol ester 8.5%
Diethylene glycol dimethyl ether 15%.
Each above-mentioned component ingredient mixing and stirring is prepared described Ca-Zn liquid composite stabilizing agent.
Embodiment 4
Ca-Zn liquid composite stabilizing agent, this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic calcium 40% of crossing alkali of calcium weight metal degree 10%
The zinc carboxylate 5.0% of zinc weight metal degree 15%
Phenylbenzene isodecyl phosphorous acid ester 10%
Diphenylpropane-1,3-dione(DPPO) 7.5%
Antioxidant 1010 3.5%
Dipentaerythritol ester 9.0%
High-boiling point kerosene 15%.
Each above-mentioned component ingredient mixing and stirring is prepared described Ca-Zn liquid composite stabilizing agent.
Embodiment 5 tubing experimental results
1, main raw material:
Polyvinyl chloride resin, SG-5, technical grade, Qilu Co., Ltd., China Petrochemical Corp;
Embodiment 1 described thermo-stabilizer, composite lubricated processing aid YFG-1/YFG-2, Hangzhou Sanye Agent Co., Ltd;
Organotin stabilizer, each is provided by domestic well-known tubing enterprise;
Inside and outside lubricant agent, ACR, CPE, CaCO
3, TiO
2, commercially available.
2, key instrument and equipment
Experiment is used mixing machine, FW177, Tianjin Tai Site instrument plant;
Torque rheometer is breathed out general RM200A, and general electrical apparatus technology limited liability company is breathed out in Harbin.
3, test recipe
Table 1 upper hose material test recipe
4, experimental result
The principle of work of torque rheometer be by the record material in confined chamber mixing process to the moment of torsion resistance of rotor and material temperature over time, come the illness that has not attacked the vital organs of the human body material in the course of processing plasticizing capacity, lubricity and deployment conditions and structural changes is crosslinked, decomposition etc.Torque rheometer can be simulated actual production equipment price process, can obtain useful data and the information of a lot of materials in the course of processing, and data presentation is directly perceived, easy analysis, accurate, can be widely used in research, contrast and the formula adjustment optimization of the plasticizing capacity, dynamic stability performance etc. of various polymeric systems, reach the effect of effectively instructing actual production.
The rheological parameter of table 2 upper hose material different stabilizers system
As can see from Figure 1, the balancing torque gap of organotin and the embodiment of the invention 1 described stablizer is little, the material temperature is basic identical, plasticizing peak time of occurrence difference change stablizer that different varieties then has been described to the influence of PVC-U system rheological performance mainly in plastifying early stage and mid-term, little to the processing characteristics influence in system later stage.And cause early stage and mid-term rheological property and the difference of parameter, major cause still is due to the difference of fusion time, plasticization temperature of different varieties stablizer, the present invention then shows as after low and time of initial plasticizing moment of torsion leans on, balancing torque also is lower than the organotin system, but can satisfy the requirement of complete processing.
Embodiment 6 pipe fitting experimental results
1, main raw material
Polyvinyl chloride resin, SG-5, technical grade, Qilu Co., Ltd., China Petrochemical Corp;
Embodiment 1 described thermo-stabilizer, composite lubricated processing aid YFJ-1/YFJ-2, Hangzhou Sanye Agent Co., Ltd;
Organotin stabilizer is provided by domestic well-known pipe fitting enterprise;
Inside and outside lubricant agent, ACR, CPE, CaCO
3, TiO
2, commercially available.
2, key instrument and equipment
Experiment is used mixing machine, FW177, Tianjin Tai Site instrument plant;
Torque rheometer is breathed out general RM200A, and general electrical apparatus technology limited liability company is breathed out in Harbin.
3, test recipe
Table 3 upper hose spare test recipe
4, test-results
Fig. 2 is the flow curve figure of upper hose spare organotin stabilizer and embodiment 1.Table 4 is the rheological parameter of upper hose spare different stabilizers system.
The rheological parameter of table 4 upper hose spare different stabilizers system
As can see from Figure 2, the balancing torque of organotin and embodiment 1 and material temperature are basic identical, and plasticizing peak time of occurrence also is more or less the same.As can see from Figure 3, we are not having broken through the extruding test or any crack occurring with the PVC upper hose spare of embodiment 1 described stablizer situ production in Zhejiang pipe fitting manufacturing enterprise, can prove that the finished product toughness of using embodiment 1 to produce is better than the stablizer of other kind.
From above experimental result, proved that embodiment 1 product can satisfy the different tubing that require, the complete processing of pipe fitting, the every index of finished product detection all can reach the GB requirement; Can substitute organotin and lead salt one package stabilizer uses in the PVC of no environmental requirement outfall sewer material, pipe fitting.So, no matter be laboratory or at thread test, embodiment 1 product fusion time is all fast than using traditional product, has reflected that embodiment 1 product has certain plasticization effect; But from detected result, stablizer does not produce very big influence to final technology; Material property: every index can satisfy the requirement of GB and relevant criterion; And from total production cost calculating, embodiment 1 product is compared with organotin stabilizer all bigger advantage.
Claims (9)
1. Ca-Zn liquid composite stabilizing agent is characterized in that this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic calcium 25%～40% of crossing alkali of calcium weight metal degree 8%～12%,
The zinc carboxylate 5%～20% of zinc weight metal degree 10%～20%,
Phosphorous acid ester 10%～30%,
Epoxy soybean oil 5%～30%,
Beta-diketone compound 2%～8%,
Oxidation inhibitor 1%～8%,
Polyol ester 5%～10%,
Solvent 10%～20%,
Above-mentioned polyol ester is selected the carboxylate of tetramethylolmethane, Dipentaerythritol, TriMethylolPropane(TMP) or Sorbitol Powder for use, and the total amount of above-mentioned each component is 100%.
2. Ca-Zn liquid composite stabilizing agent according to claim 1 is characterized in that this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic calcium 28%～38% of crossing alkali of calcium weight metal degree 8%～12%,
The zinc carboxylate 8%～18% of zinc weight metal degree 10%～20%,
Phosphorous acid ester 12%～28%,
Epoxy soybean oil 8%～28%,
Beta-diketone compound 3%～8%,
Oxidation inhibitor 2%～8%,
Polyol ester 5%～10%,
Solvent 12%～20%,
The total amount of above-mentioned each component is 100%.
3. Ca-Zn liquid composite stabilizing agent according to claim 1 is characterized in that this liquid composite stabilizing agent is made of following component by weight percentage:
The liquid carboxylic calcium 30%～35% of crossing alkali of calcium weight metal degree 8%～12%,
The zinc carboxylate 10%～15% of zinc weight metal degree 10%～20%,
Phosphorous acid ester 15%～25%,
Epoxy soybean oil 10%～25%,
Beta-diketone compound 5%～8%,
Oxidation inhibitor 3%～8%,
Polyol ester 5%～10%,
Solvent 15%～20%,
The total amount of above-mentioned each component is 100%.
4. according to claim 1 or 2 or 3 described Ca-Zn liquid composite stabilizing agents, it is characterized in that: phosphorous acid ester is selected Phenyl Di-2-ethyl Hexyl Phosphite for use, bis-phosphite, three nonyl phenyl phosphites, triisodecyl phosphite ester, phosphorous acid phenyl two isodecyl esters, phenylbenzene isodecyl phosphorous acid ester, the different monooctyl ester of phosphorous acid phenylbenzene, triphenyl phosphite, tetraphenyl dipropylene glycol diphosphites, tricresyl phosphite bay alcohol ester, three (dipropylene glycol) phosphorous acid ester, the phenylbenzene phosphorous acid ester, poly-4,4, one or both mixing in the isopropylidene diphenol C12-15 alcohol phosphorous acid ester.
5. according to claim 1 or 2 or 3 described Ca-Zn liquid composite stabilizing agents, it is characterized in that: beta-diketone compound is selected one or both mixing in diphenylpropane-1,3-dione(DPPO) and the stearyl formyl methane for use.
6. according to claim 1 or 2 or 3 described Ca-Zn liquid composite stabilizing agents, it is characterized in that: oxidation inhibitor is selected one or more in antioxidant 1076, antioxidant 1010 and the dihydroxyphenyl propane for use.
7. according to claim 1 or 2 or 3 described Ca-Zn liquid composite stabilizing agents, it is characterized in that: solvent is selected diethylene glycol dimethyl ether or high-boiling point kerosene for use.
8. pvc pipe material, it is characterized in that: this pvc pipe material has added 1%～2% weight percent such as claim 1 or 2 or 3 described Ca-Zn liquid composite stabilizing agents.
9. pvc pipe spare, it is characterized in that: this pvc pipe spare has added 2%～3% weight percent such as claim 1 or 2 or 3 described Ca-Zn liquid composite stabilizing agents.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102153824B (en) * | 2011-04-20 | 2012-11-21 | 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 |
| CN102675772A (en) * | 2012-05-10 | 2012-09-19 | 邦凯控股集团有限公司 | Anti-aging polyvinyl chloride (PVC) film |
| CN102838819B (en) * | 2012-09-21 | 2014-08-20 | 中国林业科学研究院林产化学工业研究所 | Preparation method of oil/rosin base liquid calcium-zinc composite stabilizing agent used for PVC (Polyvinyl Chloride) |
| CN102994195B (en) * | 2012-11-12 | 2014-03-26 | 关子杰 | Extreme pressure, wear resisting and friction reducing additive for lubricating oil |
| CN104045934B (en) * | 2014-06-13 | 2016-06-01 | 浙江传化华洋化工有限公司 | The synthetic method of a kind of organo-metallic phosphorous acid complex compound and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1902272A (en) * | 2003-11-12 | 2007-01-24 | 贝洛赫尔有限公司 | Stabilizing composition for thermoplastic resin compositions containing halogen |
| CN101041728A (en) * | 2006-03-23 | 2007-09-26 | 汕头市高科达有限公司 | Preparation method for (PVC) nontoxic calcium zinc heat stabilizer and uses thereof |
| CN101092492A (en) * | 2007-06-26 | 2007-12-26 | 杭州新新塑料助剂科研有限公司 | Double matching type heat stabilizer |
| CN101429289A (en) * | 2008-11-28 | 2009-05-13 | 杭州油脂化工有限公司 | Environment-friendly calcium-zinc compound stabilizer |
| CN101575422A (en) * | 2009-06-18 | 2009-11-11 | 浙江嘉澳环保科技股份有限公司 | Method for preparing environmental-friendly calcium-zinc composite liquid stabilizing agent |
-
2009
- 2009-12-16 CN CN2009101550756A patent/CN101747529B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1902272A (en) * | 2003-11-12 | 2007-01-24 | 贝洛赫尔有限公司 | Stabilizing composition for thermoplastic resin compositions containing halogen |
| CN101041728A (en) * | 2006-03-23 | 2007-09-26 | 汕头市高科达有限公司 | Preparation method for (PVC) nontoxic calcium zinc heat stabilizer and uses thereof |
| CN101092492A (en) * | 2007-06-26 | 2007-12-26 | 杭州新新塑料助剂科研有限公司 | Double matching type heat stabilizer |
| CN101429289A (en) * | 2008-11-28 | 2009-05-13 | 杭州油脂化工有限公司 | Environment-friendly calcium-zinc compound stabilizer |
| CN101575422A (en) * | 2009-06-18 | 2009-11-11 | 浙江嘉澳环保科技股份有限公司 | Method for preparing environmental-friendly calcium-zinc composite liquid stabilizing agent |
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| Title |
|---|
| 说明书3-9页. |
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