CN103627117B - Tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer and preparation method thereof - Google Patents
Tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to chemical technology field, be specifically related to a kind of tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer and preparation method thereof, be made up of the raw material of following parts by weight: tetramethylolmethane cerium 30-50 part, barium stearate 10-15 part, calcium stearate 20-30 part, lubricant 20-30 part, auxiliary heat stabilizer 10-15 part.Preparation method first adds tetramethylolmethane cerium, barium stearate and calcium stearate in reactor fully to mix, the material mixed is added in kneader at 100-120 DEG C, mediates 20-30min, then in kneader, lubricant and auxiliary heat stabilizer is added, mediate and stir 30-40min, discharging compressing tablet, screening, packaging, to obtain final product.Composite thermal stabilizer prepared by the present invention have not easily separate out, stabilising effect is good, raw material is easy to get, the feature of cheap, asepsis environment-protecting.Preparation method of the present invention is pollution-free, energy consumption is low, scientific and reasonable, simple.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer and preparation method thereof.
Background technology
PVC(polyvinyl chloride) be apply extremely extensively material, it is after practical breakthrough in 1933, and along with industrialized paces, its application aspect is more and more wider, and annual production is increasing.Although the purposes of PVC is extremely wide, its work-ing life is but very short, causes very large waste.Scientists is attempting the various method extending PVC work-ing life always, and wherein adding thermo-stabilizer is a kind of cost-effective method.Thermo-stabilizer is a kind of chemical assistant, and it can suppress PVC in machine-shaping and use procedure due to heat, light action and the degraded that causes and variable color.Conventional thermo-stabilizer has the large class of lead salt stabilizer, metal soap, organo-tin compound, organic stabilizer and one package stabilizer five.
Lead salts thermo-stabilizer is the stablizer developed the earliest, there is Product Process simple, the advantages such as cheap, performance is outstanding, but this type of heavy metal stabilizer requires the impact improved constantly by RolS instruction and EUP instruction technique barrier and Chinese environmental protection, the poisonous thermo-stabilizers such as leaded, cadmium are banned gradually, and the organic tinbase of environment-friendly type, rare earth class and organic compound base thermo-stabilizer will obtain new development.Organotin is highly effective thermo-stabilizer, and transparent article can be made to keep very high transparency and consumption is less, but the shortcoming that organotin cost is high, peculiar smell is large limits its application to a certain extent.Rare earth class thermo-stabilizer is the New Heat Stabilizer that development in recent years is got up, and has the advantages such as nontoxic, efficient, multi-functional, be applicable to soft, hard and transparent and opaque PVC product, but its cost is high, does not have wide spectrum suitability.Organic compound base thermo-stabilizer kind is few, low by the degree of recognition, is difficult to put it over, and therefore, organic tinbase and rare earth class stablizer will be the heat stabilizer systems most with development potentiality.In addition, because organic tinbase exists the weakness such as price is high, peculiar smell is large, so, so rare earth class stabilizer has more development space.
But, be used alone rare earth class thermo-stabilizer and there is again the high defect of price, so present people start trial prepare metal polyvalent alcohol alkali thermo-stabilizer.Patent of invention CN201110099669.7 discloses a kind of preparation method of environment-friendly high-efficiency composite thermal stabilizer, and the method is by zinc three salt (tetramethylolmethane and zinc oxide reaction obtain), calcium stearate, lubricant and the auxiliary heat stabilizer composite mixture obtained according to a certain percentage.The composite thermal stabilizer adding zinc three salt can extend the heat-stable time of PVC, improves initial coloring, reduces the balancing torque of PVC product, improves processing characteristics, reduces costs.But add zinc three salt time, PVC initial stage whiteness and long-term thermal stability performance (only 60min) still undesirable.
Patent of invention CN201010572210.X discloses a kind of method of preparing glyzinc under high pressure, this invention is by zinc oxide and glycerine heating reflux reaction according to a certain percentage, after back flow reaction completes, reaction mixture is moved in autoclave and continue reaction, obtain glycerin zinc, gained glycerin zinc can be used for novel Non-toxicHeat Stabilizer for Polyvinyl Chloride.Adopt this technology to prepare glycerin zinc operating process long, and adopt the reaction under high pressure having certain danger, therefore, the not easily scale operation of this technology.
Patent of invention CN201110187680.9 discloses a kind of preparation of glyceryl calcium/zinc composite heat stabilizer, and this composite thermal stabilizer is at normal temperatures and pressures, mixes obtained by glycerine calcium, glycerin zinc, auxiliary stabilizer according to proportioning.This composite thermal stabilizer can improve thermostability and the stain resistance of polyvinyl chloride, and glyceryl calcium/zinc composite heat stabilizer overcomes the shortcomings such as poisonous, the heavy metal contamination of traditional thermo-stabilizer, thermal stability result be not good, there is nontoxic, environmental protection, heavy metal free, the advantage such as cheap, be a kind of composite thermal stabilizer efficiently, there is good application prospect.This glyceryl calcium/zinc composite heat stabilizer adds to inside PVC, and relative to pure glycerin zinc, its thermostability makes moderate progress, but sees its thermo-stabilizer formula, finds no corresponding lubricant, and thus its dynamic machining performance should be short of to some extent.
The preparation method of existing multiple non-toxic heat stabilizer, but the thermo-stabilizer of preparation otherwise initial stage thermostable effect undesirable, or thoroughly do not change " zinc burning " phenomenon, otherwise be exactly high expensive, strongly limit applying of asepsis environment-protecting thermo-stabilizer.
Summary of the invention
The object of this invention is to provide a kind of tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer, raw material be easy to get, cheap, asepsis environment-protecting, not easily separate out, stabilising effect is good; Invention also provides the preparation method of tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer, scientific and reasonable, simple, pollution-free, energy consumption is low.
Tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer of the present invention, be made up of the raw material of following parts by weight:
The preparation method of described tetramethylolmethane cerium takes 20-35 part tetramethylolmethane and 21-38 part cerous carbonate, the two is fully pulverized and mixed with pulverizer, add reactor, add 0.1-0.4 part acetic acid again to stir, oil bath is heated to 170-190 DEG C, heats while stirring, and reacts after 4-5 hour, material is taken out cooling, after pulverizing and get final product; With weight parts.
Described lubricant is paraffin.
Described auxiliary heat stabilizer is the mixture of stearoyl benzoyl methane, triphenyl phosphite and dihydroxyphenyl propane.
The mass ratio of described stearoyl benzoyl methane, triphenyl phosphite and dihydroxyphenyl propane is 4-9:3:3.
The preparation method of tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer of the present invention first adds tetramethylolmethane cerium, barium stearate and calcium stearate in reactor fully to mix, the material mixed is added in kneader at 100-120 DEG C, mediates 20-30min, then in kneader, lubricant and auxiliary heat stabilizer is added, mediate and stir 30-40min, discharging compressing tablet, screening, packaging, to obtain final product.
Composite thermal stabilizer prepared by interpolation the present invention can improve the thermostability of polyvinyl chloride, and static heat stability test result shows, the polyvinyl chloride (PVC) RESINS heat-stable time adding this stablizer can reach 60min.Under 180 ± 1 DEG C of conditions, PVC not only has good anti-initial coloring, and still can not blackening after being heated to 90min.
The present invention compared with prior art, has following beneficial effect:
Composite thermal stabilizer prepared by the present invention, not only there are comparatively ideal initial stage form and aspect, and revolutionize " zinc burning " phenomenon, long-term thermal stability is excellent, overall thermal stability is better than traditional lead salt, have not easily separate out, stabilising effect is good, raw material is easy to get, the feature of cheap, asepsis environment-protecting.Preparation method of the present invention is pollution-free, energy consumption is low, scientific and reasonable, simple.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
The preparation of tetramethylolmethane cerium: take 25kg tetramethylolmethane and 28kg cerous carbonate, the two is fully pulverized and mixed with pulverizer, add reactor, add 0.1kg acetic acid again to stir, oil bath is heated to 190 DEG C, heats while stirring, and reacts after 5 hours, material is taken out cooling, after pulverizing, namely obtains tetramethylolmethane cerium.
The preparation of tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer: first 42kg tetramethylolmethane cerium, 12kg barium stearate and 20kg calcium stearate are added in reactor and fully mix, get mixture, add in kneader and mediate 25min at 100 DEG C, then in kneader, 25kg paraffin, 4kg stearoyl benzoyl methane, 3kg triphenyl phosphite and 3kg dihydroxyphenyl propane is added successively, mediate and stir 30min, discharging screening, packaging, obtain the finished product.
Embodiment 2
The preparation of tetramethylolmethane cerium: take 20kg tetramethylolmethane and 21kg cerous carbonate, the two is fully pulverized and mixed with pulverizer, add reactor, add 0.2kg acetic acid again to stir, oil bath is heated to 190 DEG C, heats while stirring, and reacts after 4 hours, material is taken out cooling, after pulverizing, namely obtains tetramethylolmethane cerium.
The preparation of tetramethylolmethane cerium base PVC environment-friendly high-efficiency composite thermal stabilizer: first 30kg tetramethylolmethane cerium, 10kg barium stearate and 30kg calcium stearate are added in reactor and fully mix, get mixture, add in kneader and mediate 30min at 100 DEG C, then in kneader, 30kg paraffin, 4kg stearoyl benzoyl methane, 3kg triphenyl phosphite and 3kg dihydroxyphenyl propane is added successively, mediate and stir 35min, discharging screening, packaging, obtain the finished product.
Embodiment 3
The preparation of tetramethylolmethane cerium: take 35kg tetramethylolmethane and 38kg cerous carbonate, the two is fully pulverized and mixed with pulverizer, add reactor, add 0.4kg acetic acid again to stir, oil bath is heated to 170 DEG C, heats while stirring, and reacts after 4.5 hours, material is taken out cooling, after pulverizing, namely obtains tetramethylolmethane cerium.
The preparation of tetramethylolmethane cerium base PVC environment-friendly high-efficiency composite thermal stabilizer: first 40kg tetramethylolmethane cerium, 15kg barium stearate and 25kg calcium stearate are added in reactor and fully mix, get mixture, add in kneader and mediate 20min at 120 DEG C, then in kneader, 20kg paraffin, 6kg stearoyl benzoyl methane, 3kg triphenyl phosphite and 3kg dihydroxyphenyl propane is added successively, mediate and stir 40min, discharging screening, packaging, obtain the finished product.
Embodiment 4
The preparation of tetramethylolmethane cerium: take 30kg tetramethylolmethane and 32kg cerous carbonate, the two is fully pulverized and mixed with pulverizer, add reactor, add 0.1kg acetic acid again to stir, oil bath is heated to 180 DEG C, heats while stirring, and reacts after 5 hours, material is taken out cooling, after pulverizing, namely obtains tetramethylolmethane cerium.
Tetramethylolmethane cerium base PVC environment-friendly high-efficiency composite thermal stabilizer composite: first 50kg tetramethylolmethane cerium, 14kg barium stearate and 20kg calcium stearate are added in reactor and fully mix, get mixture, add in kneader and mediate 30min at 120 DEG C, then in kneader, 25kg paraffin, 9kg stearoyl benzoyl methane, 3kg triphenyl phosphite and 3kg dihydroxyphenyl propane is added successively, mediate and stir 30min, discharging screening, packaging, obtain the finished product.
Congo Red test:
Above-described embodiment 1,2,3 and 4 four kind of composite thermal stabilizer are added in 100 mass parts PVC respectively by 4 mass parts, then adds 50 mass parts dimixo-octyl phthalates (DOP), 5 mass parts TiO
2, 5 mass parts CaCO
3, twin-roll mixing 5 minutes at 180 DEG C, makes the laminar sample that thickness is 1mm.Sample is cut into small shreds, and under 180 ± 1 DEG C of conditions, do Congo Red test, experimental result is in table 1.Wherein, pure PVC is comparative example.
Table 1 Congo Red test
Static heat senile experiment:
By above-mentioned obtained PVC thin slice, be cut into the little test piece of 1cm × 1cm, under 180 ± 1 DEG C of conditions, do static heat senile experiment, experimental result is in table 2.Wherein, pure PVC is comparative example.
Table 2 static heat senile experiment
| Formula | Heat-stable time |
| Pure PVC | 12min |
| Embodiment 1 | 105min |
| Embodiment 2 | 100min |
| Embodiment 3 | 115min |
| Embodiment 4 | 120min |
Result shows, and adds the long-term thermal stability performance that tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer obviously can improve PVC.
Dynamic machining is tested:
By above-described embodiment 1,2,3,4 four kind of composite thermal stabilizer add respectively in 100 mass parts PVC by 4 mass parts, then add 50 mass parts dimixo-octyl phthalates (DOP), 5 mass parts TiO
2, 5 mass parts CaCO
3, be made into dry blend.Get the dynamic machining performance that 60g dry blend uses Haake torque rheometer test compound thermo-stabilizer.Rotating speed 30rpm, temperature 180 DEG C.
Table 3 is dynamic machining performance test results.Result shows, and tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer obviously can promote plasticizing, reduces balancing torque, dynamic machining excellent property.
Table 3 composite thermal stabilizer affects PVC processing characteristics
Whiteness is tested:
Use above-described embodiment 1,2,3 and 4, add in 100 parts of PVC, add 50 parts of dimixo-octyl phthalates (DOP) again, then by GB GB2113-82 " plastics whiteness experimental technique ", four kinds of PVC plastic of preparation are carried out heat-resisting whiteness experiment, test piece being placed on by whiteness is the relative whiteness value tested in the verified whiteness instrument of standard white body of 85%, and table 4 is whiteness experimental results.
Table 4 whiteness experimental result
Can find from table 4, prepared tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer has outstanding initial stage form and aspect and long-term thermal stability.
Claims (5)
1. a tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer, is characterized in that being made up of the raw material of following parts by weight:
The preparation method of described tetramethylolmethane cerium takes 20-35 part tetramethylolmethane and 21-38 part cerous carbonate, the two is fully pulverized and mixed with pulverizer, add reactor, add 0.1-0.4 part acetic acid again to stir, oil bath is heated to 170-190 DEG C, heats while stirring, and reacts after 4-5 hour, material is taken out cooling, after pulverizing and get final product.
2. tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer according to claim 1, is characterized in that described lubricant is paraffin.
3. tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer according to claim 1, is characterized in that described auxiliary heat stabilizer is the mixture of stearoyl benzoyl methane, triphenyl phosphite and dihydroxyphenyl propane.
4. tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer according to claim 3, is characterized in that the mass ratio of described stearoyl benzoyl methane, triphenyl phosphite and dihydroxyphenyl propane is 4-9:3:3.
5. the preparation method of the arbitrary described tetramethylolmethane cerium base PVC high efficiency composition thermo-stabilizer of claim 1-4, it is characterized in that first tetramethylolmethane cerium, barium stearate and calcium stearate being added in reactor fully mixing, the material mixed is added in kneader at 100-120 DEG C, mediates 20-30min, then in kneader, lubricant and auxiliary heat stabilizer is added, mediate and stir 30-40min, discharging compressing tablet, screening, packaging, to obtain final product.
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| CN104312056A (en) * | 2014-11-13 | 2015-01-28 | 苏州誉之铖贸易有限责任公司 | Organic acid and rare earth composite heat stabilizer for PVC (polyvinyl chloride) |
| CN106316790A (en) * | 2016-08-18 | 2017-01-11 | 河源市鑫达科技有限公司 | Process for synthesizing zinc pentaerythritol in heat stabilizer |
| CN106893137A (en) * | 2017-03-27 | 2017-06-27 | 包头稀土研究院 | Polyalcohol rare earth complex heat stabilizer |
| CN109438235B (en) * | 2018-09-17 | 2022-02-22 | 山东理工大学 | Preparation method of 1, 2-cyclohexanedicarboxylic acid dipentaerythritol ester zinc metal alkoxide |
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| CN103073820A (en) * | 2013-01-18 | 2013-05-01 | 内蒙古科技大学 | Rare earth composite heat stabilizer for PVC |
| CN103073826A (en) * | 2013-02-01 | 2013-05-01 | 唐山师范学院 | Rare-earth composite heat stabilizer for hard PVC (Polyvinyl Chloride) |
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| CN102153824A (en) * | 2011-04-20 | 2011-08-17 | 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 |
| CN103073820A (en) * | 2013-01-18 | 2013-05-01 | 内蒙古科技大学 | Rare earth composite heat stabilizer for PVC |
| CN103073826A (en) * | 2013-02-01 | 2013-05-01 | 唐山师范学院 | Rare-earth composite heat stabilizer for hard PVC (Polyvinyl Chloride) |
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