CN101724210B - Stabilizing agent for processing PVC transparent sheet and preparation method and application thereof - Google Patents
Stabilizing agent for processing PVC transparent sheet and preparation method and application thereof Download PDFInfo
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- CN101724210B CN101724210B CN2009101571150A CN200910157115A CN101724210B CN 101724210 B CN101724210 B CN 101724210B CN 2009101571150 A CN2009101571150 A CN 2009101571150A CN 200910157115 A CN200910157115 A CN 200910157115A CN 101724210 B CN101724210 B CN 101724210B
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Abstract
The invention discloses a stabilizing agent for processing a PVC transparent sheet and a preparation method and the application thereof; the stabilizing agent is composed of (R2-OOC-R1-COO-)2Ca2+ and (R2-OOC-R1-COO-)2Zn2+; wherein R1 is C2-C16 alkylene, C6-C16 arylene or C6-C16 cycloalkylene; R2 is C2-C16 alkyl, or C6-C16 aryl or C6-C16 naphthenic base. In the invention, fundamental change is carried out on an organic ligand, the traditional thinking line that long chain fatty acid is used as the organic ligand of calcium-zinc soap is broken through, the design and the synthesis lead the invention to have a novel calcium-zinc ligand with (poly) ester structure, and the stabilizing agent has good compatibility with PVC, so as to greatly improve the transparency of the PVC sheet.
Description
Technical field
The present invention relates to the macromolecule chemical industry technical field, relate in particular to the stablizer of a kind of PVC of being used for.
Background technology
SE (PVC) is one of the world's five big general-purpose plastics, and its global output is only second to Vilaterm and occupies second.At present the PVC product be divided into mainly that soft opaque, soft transparent, hard are opaque, four big types of hard transparents, wherein hard transparent PVC goods are new variety that development in recent years is got up.Compare with most of general-purpose plastics, PVC has good weatherability, fire-retardant and cheap advantage.
The gordian technique that eco-friendly hard transparent PVC produces is high performance thermo-stabilizer.Facts have proved that in PVC machine-shaping process, when temperature reached 90 ℃, pyrolysis promptly took place PVC; When temperature reached 120 ℃, tangible pyrolysis took place.Thermolysis is meant that the PVC main chain is heated and sloughs HCl, forms two keys; When the number of conjugated double bond reaches 5, the beginning Show Color; When the number of conjugated double bond reached 7-11, the color of PVC transferred dark-brown to until black; Simultaneously, take off two keys fracture under heat, oxygen effect that HCl produces, cause polymer degradation, mechanical property is descended.Therefore, in the forming process of various PVC goods, all need add the degraded that suitable thermo-stabilizer prevents PVC.Particularly in the hard PVC processing products, the use of softening agent is restricted, and need carry out machine-shaping more than the PVC melt temperature (136 ℃) even under 190 ℃ the high temperature, so the high temperature heat-resistant stablizer becomes indispensable auxiliary agent in the hard PVC processing.
Metal soap thermal stabilizers mainly is Ba, Ca, Mg, Cd, the Zn salt of longer chain fatty acid.The mechanism that metal soap thermal stabilizers plays a role is: the fatty acid radical part of (1) metals ion can replace active chlorallylene, makes elementary radical be difficult to form, and the Kettenreaktion of taking off HCl is stopped; (2) metals ion can absorb the HCl that the PVC thermolysis forms, and suppresses the development of degradation process.When adopting lipid acid, absorb ability Ba＜Ca＜Mg＜Cd＜Zn of HCl as organic ligand.Because Cd and Zn ability rapid absorption HCl, so Cd soap and Zn soap type thermal stabilizing agent can suppress initial coloration, the low-temperature heat good stability; But absorb the CdCl that HCl produces
2Soap and ZnCl
2Be Lewis acid, PVC is taken off HCl has katalysis.ZnCl
2Katalysis is remarkable, causes that PVC at high temperature decomposes variable color rapidly, and this phenomenon is called as " zinc burning ".Though Ba, Ca, Mg soap type thermal stabilizing agent do not exist zinc to burn problem, low because of absorbing the HCl ability, initial coloring is poor, so two type thermal stabilizing agents often are used, makes composition metal soap thermo-stabilizer.Metallic soap heat stabilizing system commonly used has: barium-cadmium, barium-cadmium-zinc, barium-zinc, calcium-zinc and the system that adopts rare earth metal; But cadmium is poisonous; Do not meet environmental requirement, withdraw from gradually, and the stablizer of rare earth metal class is because cost is high, resource-constrained also is unfavorable for extensive employing.
That calcium-zinc compound system has is nontoxic, environmental protection, advantages of cheap price, has become research and development focus in recent years, and a lot of RPs and patent report are arranged.According to statistics, calcium-Zn composite heat stabilizer has accounted for more than 30% of home market total amount.But the nonpolar structure of the similar paraffin of aliphatic chain of lipid acid part in traditional calcium-zinc soap type thermal stabilizing agent, obvious with the polar structure difference of PVC, consistency is not good, be prone to produce micron-scale phase separation, so the goods transparency haves much room for improvement.In addition, because calcium-ability that zinc absorbs HCl is not as lead-Xi, use is to add more a large amount of auxiliary heat stabilizers, increase the trend that is separated.Therefore calcium-Zn composite heat stabilizer the system that satisfies the transparent PVC processing products is still waiting research and development.
Summary of the invention
The present invention provides the high stablizer that is used for processing PVC transparent sheet of transparency after a kind of good stability, environmental protection, the interpolation.
A kind of stablizer that is used for processing PVC transparent sheet is by [R
2-OOC-R
1-COO-]
2Ca
2+[R
2-OOC-R
1-COO-]
2Zn
2+Form.
R wherein
1Be C
2～C
22Alkylidene group, C
2～C
22Alkenylene, C
6～C
22Arylidene or C
6～C
22Cycloalkylidene;
R
2Be C
2～C
22Alkyl or C
6～C
22Aryl or C
6～C
22Naphthenic base;
For example:
R
1Can be-(CH
2)
2-,-(CH
2)
3-,-(CH
2)
4-,-(CH
2)
6-or
Deng;
R
2Can be (CH
2)
2-, (CH
2)
3-, (CH
2)
4-, (CH
2)
6-or
Deng.
As preferably, R
1Be C
4～C
15Alkylidene group or C
2～C
14Alkenylene; R
2Be C
4～C
14Alkyl; And R
1And R
2The total atom number be 8～24.
Consider the cost of raw material, preferred as further, R
1Be C
4, C
6Or C
10～C
15Alkylidene group or C
2～C
14Alkenylene; R
2Be C
4, C
5, C
6Or C
8～C
14Alkyl; And R
1And R
2The total atom number be 8～24.
Available technology adopting calcium stearate and Zinic stearas are as thermo-stabilizer, because calcium stearate and Zinic stearas all are to contain C
17The carboxylate salt of long aliphatic chain, nonpolar long aliphatic chain and polarity PVC chain consistency are bad, cause the structure microphase-separated, influence transparency.Calcium stearate and Zinic stearas fusing point are respectively: 140-160 ℃ and 118-125 ℃, this melting range is fit to PVC processing, so preferred R among the present invention
1And R
2The total atom number be 8～24, [R in the stablizer like this
2-OOC-R
1-COO-]
2Ca
2+[R
2-OOC-R
1-COO-]
2Zn
2+Melting range be respectively 130-160 ℃ with 120-150 ℃, melting range and calcium stearate zinc are similar, are fit to PVC processing, but the while can obviously be improved the PVC transparency.
On the contrary, if R
1And R
2Alkyl is too big or too little, and institute's synthetic thermo-stabilizer fusing point can be very high or very low, is unfavorable for PVC processing.130-160 ℃ of the preferred calcium thermo-stabilizer of the present invention fusing point, and 120-150 ℃ of the zinc heat stabilizer fusing point of the present invention choosing, approaching with the PVC melt temperature, processing preferably.
Although R
1And R
2Independent separately, can be identical also can be inequality, but [R
2-OOC-R
1-COO-]
2Ca
2+In R
1[R
2-OOC-R
1-COO-]
2Zn
2+In R
1Be identical, [R in like manner
2-OOC-R
1-COO-]
2Ca
2+In R
2[R
2-OOC-R
1-COO-]
2Zn
2+In R
2Be identical.
[R in the stablizer
2-OOC-R
1-COO-]
2Ca
2+[R
2-OOC-R
1-COO-]
2Zn
2+Mol ratio be 1: 1.2～2.5, preferred 1: 1.5, appropriate C a, Zn ratio more helped bringing into play both synergies.
Stablizer of the present invention is that monoesters fatty acid calcium and zinc can be by R
2-OOC-R
1-COOH carries out calcium zinc impregnation reaction and makes.
R
2-OOC-R
1-COOH can be by R
2-OH and HOOC-R
1-COOH makes through esterification, through the ratio that control feeds intake, guarantees that principal product is R
2-OOC-R
1-COOH.
Monoesters fatty acid calcium and zinc compound method:
Add R in the reactor drum
2-OH and HOOC-R
1-COOH and account for R
2The catalyzer of 0.5%～2% (preferred 1%) of-OH quality; Catalyzer can be selected alkylsulphonic acid etc. for use; Timing sampling is measured acid number and is calculated esterification yield. and when acid number changes less than 1mgKOH/g, be regarded as the single-esterification terminal point, esterification yield is measured with reference to GB GB6489.2-86.
HOOC-R
1-COOH and R
2The mol ratio of-OH is 1: 1～1.05, general 115～150 ℃ preferred 140 ℃ of the temperature of esterification, and the reaction times confirms that according to sampling and measuring about general 4h, esterification yield can reach 98%.
After treating that single-esterification fully, adopt the replacement(metathesis)reaction principle, directly add suitable quantity of water and system is warming up to more than 80 ℃, add the sodium hydroxide reaction and generate rare soda soap solution, generate calcium or zinc soap deposition adding the reaction of calcium chloride or zinc oxide aqueous solution then.Deposition is through washing, press filtration (or drying), dry product monoesters fatty acid calcium or the zinc of getting.Also can adopt the raw material of other calcics in the prior art or zinc to react.
Reaction principle can use following reaction formula to express:
In the stablizer of the present invention; Adopting organic dibasic acid and monohydroxy-alcohol is raw material; At the low-molecular-weight polyester of p-methyl benzenesulfonic acid, MOX super acids, inferior tin class catalyst action realization condensation polymerization (esterification) anamorphic zone carboxyl end group, control the molecular weight of product through the functionality ratio of controlling acid and alcohol.
Control indexs such as the viscosity of the polyester that obtains, fusing point through selecting the acid and the chemical structure of alcohol.Again according to the acid number of synthetic ester; Mix with quicklime, the zinc oxide (the perhaps calcium of other type, zinc raw material) of stoichiometry coupling; Under the condition of heated and stirred, form polyester type calcium zinc soap product; Crude product after washing, dehydration, drying treatment, the indexs such as acid number, viscosity, fusing point, thermostability, refractive index, colour, calcium, zinc content of test product.The present invention utilizes carboxyl end group to form the zinc calcium soap, compares existing calcium-zinc compound system stablizer and can significantly improve the transparency.
The present invention also provides the application of described stablizer in processing PVC transparent sheet.Its addition is 1～3% of a PVC quality, preferred 1.4%.
The present invention also provides a kind of PVC clear sheet, contains described stablizer.The transmittance of PVC clear sheet (%) (thickness 0.8-1.0mm):>=90, mist degree (thickness 0.11-0.30mm) :≤6.0.
The key problem in technology that solves hard PVC transparency in the prior art is that the design of organic calcium-zinc part is synthetic, and the nonpolar fatty chain of Triple Pressed Stearic Acid part and polar PVC can not very compatible in traditional calcium zinc soap stablizer, directly influence transparency.The present invention carries out basic change on organic ligand; Broken through traditional with the thinking of longer chain fatty acid as the organic ligand of calcium-zinc soap; Design and synthetic new calcium-zinc part with (gathering) ester structure make novel organic calcium zinc than traditional fatty acid calcium-zinc and PVC better consistency arranged.
Embodiment
The preparation of embodiment 1 thermo-stabilizer
Add hexanodioic acid 146 grams, propyl carbinol 74 grams and p-methyl benzenesulfonic acid 2.2 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield. and when acid number changes less than 1mgKOH/g, be regarded as the single-esterification terminal point, reacted altogether 4 hours, obtain Succinic Acid n-dodecanol ester; Directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 grams then, reaction generates calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 2 thermo-stabilizers
Add hexanodioic acid 146 grams, n-Octanol 130 grams and p-methyl benzenesulfonic acid 2.7 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield. and when acid number changes less than 1mgKOH/g, be regarded as the single-esterification terminal point, reacted altogether 4 hours, obtain Succinic Acid n-dodecanol ester; Directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 grams then, reaction generates calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 3 thermo-stabilizers
Add hexanodioic acid 146 grams, positive undecyl alcohol 172 grams and p-methyl benzenesulfonic acid 3.2 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained Succinic Acid n-dodecanol ester, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 4 stablizers
Add hexanodioic acid 146 grams, positive tetradecyl alcohol 214 grams and p-methyl benzenesulfonic acid 3.6 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained Succinic Acid n-dodecanol ester, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 5 thermo-stabilizers
Add Succinic Acid 118 grams, propyl carbinol 74 grams and p-methyl benzenesulfonic acid 2 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained Succinic Acid n-dodecanol ester, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 6 thermo-stabilizers
Add Succinic Acid 118 grams, Pentyl alcohol 88 grams and p-methyl benzenesulfonic acid 2 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained Succinic Acid n-dodecanol ester, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 7 thermo-stabilizers
Add Succinic Acid 118 grams, n-Octanol 130 grams and p-methyl benzenesulfonic acid 2.5 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained Succinic Acid n-dodecanol ester, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium or deposition.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 8 thermo-stabilizers
Add Succinic Acid 118 grams, positive undecyl alcohol 172 grams and p-methyl benzenesulfonic acid 2.8 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 9 thermo-stabilizers
Add Succinic Acid 118 grams, positive tetradecyl alcohol 214 grams and p-methyl benzenesulfonic acid 3 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 10 thermo-stabilizers
Add sebacic acid 202 grams, propyl carbinol 74 grams and p-methyl benzenesulfonic acid 2.7 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium or deposition.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 11 thermo-stabilizers
Add sebacic acid 202 grams, n-Octanol 130 grams and p-methyl benzenesulfonic acid 2.3 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 12 thermo-stabilizers
Add sebacic acid 202 grams, positive tetradecyl alcohol 214 grams and p-methyl benzenesulfonic acid 4.1 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 13 thermo-stabilizers
Add dodecanedioic acid 230 grams, propyl carbinol 74 grams and p-methyl benzenesulfonic acid 3.0 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 14 thermo-stabilizers
Add dodecanedioic acid 230 grams, n-Octanol 130 grams and p-methyl benzenesulfonic acid 3.6 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield. and when acid number changes less than 1mgKOH/g, be regarded as the single-esterification terminal point, reacted altogether 4 hours, obtain the positive tetradecyl alcohol ester of Succinic Acid; Directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 grams then, reaction generates calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 15 thermo-stabilizers
Add dodecanedioic acid 230 grams, positive tetradecyl alcohol 214 grams and p-methyl benzenesulfonic acid 4.3 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 16 thermo-stabilizers
Add maleic acid 116 grams, propyl carbinol 74 grams and p-methyl benzenesulfonic acid 1.9 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 17 thermo-stabilizers
Add maleic acid 116 grams, n-Octanol 130 grams and p-methyl benzenesulfonic acid 2.5 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
The preparation of embodiment 17 stablizers
Add maleic acid 116 grams, positive tetradecyl alcohol 214 grams and p-methyl benzenesulfonic acid 2.5 grams in the reactor drum; Stirring is warming up to 140 ℃ and carries out esterification; Timing sampling is measured acid number and is calculated esterification yield., acid number is regarded as the single-esterification terminal point when changing less than 1mgKOH/g; Reacted altogether 4 hours, and obtained the positive tetradecyl alcohol ester of Succinic Acid, directly add entry 1000ml in the esterification system and system is warming up to 50 ℃; Add sodium hydroxide 20 gram reactions and generate rare soda soap solution, add calcium chloride 55 gram reactions then and generate calcium soap precipitates.Deposition is through washing, filtration, the dry product monoesters fatty acid calcium that gets.
Same condition only is changed to zinc oxide 41 grams with calcium chloride 55 gram, can make the monoesters fatty acid zinc, and the monoesters fatty acid zinc mixes with above-mentioned monoesters fatty acid calcium and obtains monoesters fatty acid calcium Zn composite heat stabilizer.
Performance test
By the mass fraction prescription batch mixes in each table good after, mixing 5min in 160 ℃ of pair roller mills processes thick hard PVC sheet of 0.8mm and flexible PVC sheet.Measure the priming color (being that test piece is without the preceding color of baking oven baking) and the transparency of test piece, then test piece is put into 170 ℃ baking oven, whenever change at a distance from 10min sampling observation.
In all test cases, thermal stability carries out with reference to ASTM D2115-67; Transmittance and mist degree are undertaken by GB 2410-1980 and GB 4455-2006.
Test case 1～6
Table 1
Annotate: the polyvinyl chloride resin of test case 1～3 is horminess PVC formula; The polyvinyl chloride resin of test case 4～6 is for being the flexible PVC prescription.DOP (DOP) is the PVC common plasticizers, the difference of soft hard PVC mainly the content of DOP what.It is soft that content is exactly more, otherwise be exactly hard.
Can find out from table 1; It is poorer slightly than capital tin 8831 that the monoesters fatty acid calcium Zn composite heat stabilizer initial stage of the present invention is suppressed the metachrosis of PVC; But the long term inhibition metachrosis is suitable with it; It can also be seen that from table 1 monoesters fatty acid calcium Zn composite heat stabilizer suppresses the PVC metachrosis and is better than the calcium stearate Zn composite heat stabilizer.
Monoesters fatty acid calcium Zn composite heat stabilizer is to the influence of the PVC slide transparency:
Can find out that from table 1 adopt monoesters fatty acid calcium Zn composite heat stabilizer, the transmittance of slide is higher, mist degree is lower, and is suitable basically when making thermo-stabilizer with capital tin 8831.This mainly is because monoesters fatty acid calcium Zn composite heat stabilizer has the ester structure close with PVC polarity, and is good with close the two consistency that makes of polarity of PVC, has solved the problem of the transparency difference that causes because of being separated.The transmittance and the mist degree of monoesters fatty acid calcium Zn composite heat stabilizer obviously are superior to the calcium stearate Zn composite heat stabilizer.
Test case 7～12
Table 2
Annotate: the polyvinyl chloride resin of test case 7～9 is horminess PVC formula; The polyvinyl chloride resin of test case 10～12 is for being the flexible PVC prescription.
Can find out that from table 2 metachrosis of three kinds of thermo-stabilizer initial stage inhibition PVC is suitable, but long term inhibition metachrosis monoesters fatty acid calcium Zn composite heat stabilizer is better than calcium stearate Zn composite heat stabilizer and rare earth thermal stabilizer Triple Pressed Stearic Acid lanthanum.
Monoesters fatty acid calcium Zn composite heat stabilizer is to the influence of the PVC slide transparency:
Can find out from table 2; Adopt monoesters fatty acid calcium Zn composite heat stabilizer, the transmittance of slide is higher, and mist degree is lower; Obviously be superior to calcium stearate Zn composite heat stabilizer and rare earth thermal stabilizer Triple Pressed Stearic Acid lanthanum, the calcium stearate Zn composite heat stabilizer transparency is the poorest.This mainly is because stearic long aliphatic chain is nonpolar, and is poor with the polar chain consistency of PVC, causes micron-scale phase separation, influences the PVC transparency.
Test case 13～18
Table 3
Annotate: the polyvinyl chloride resin of test case 13～15 is horminess PVC formula; The polyvinyl chloride resin of test case 16～18 is for being the flexible PVC prescription.
Can find out that from table 3 metachrosis of monoesters fatty acid calcium Zn composite heat stabilizer initial stage and long term inhibition PVC is suitable with mercaptan antimony, but the long term inhibition metachrosis is superior to the calcium stearate Zn composite heat stabilizer.
Monoesters fatty acid calcium Zn composite heat stabilizer is to the influence of the PVC slide transparency:
Can find out that from table 3 adopt monoesters fatty acid calcium Zn composite heat stabilizer, the transmittance of slide is a little more than mercaptan antimony, mist degree obviously is superior to the calcium stearate Zn composite heat stabilizer a little less than mercaptan antimony.
Test case 19～24
Table 4
Annotate: the polyvinyl chloride resin of test case 19～21 is horminess PVC formula; The polyvinyl chloride resin of test case 22～24 is for being the flexible PVC prescription.
Can find out that from table 4 metachrosis of monoesters fatty acid calcium Zn composite heat stabilizer initial stage and long term inhibition PVC is suitable with three fumaric acid benzene methyl lanthanums, but the long term inhibition metachrosis is superior to the calcium stearate Zn composite heat stabilizer.
Monoesters fatty acid calcium Zn composite heat stabilizer is to the influence of the PVC slide transparency:
Can find out that from table 4 adopt monoesters fatty acid calcium Zn composite heat stabilizer, the transmittance of slide is also a little more than three fumaric acid benzene methyl lanthanums, mist degree obviously is superior to the calcium stearate Zn composite heat stabilizer a little less than three fumaric acid benzene methyl lanthanums.
Test case 25～30
Table 5
Annotate: the polyvinyl chloride resin of test case 25～27 is horminess PVC formula; The polyvinyl chloride resin of test case 28～30 is for being the flexible PVC prescription.
Can find out that from table 5 metachrosis of initial stage and long term inhibition PVC is suitable with toxilic acid list dihydroxyphenyl propane ester rare earth, but the long term inhibition metachrosis is superior to the calcium stearate Zn composite heat stabilizer.
Monoesters fatty acid calcium Zn composite heat stabilizer is to the influence of the PVC slide transparency:
Can find out that from table 5 adopt monoesters fatty acid calcium Zn composite heat stabilizer, the transmittance of slide is a little more than toxilic acid list dihydroxyphenyl propane ester rare earth, mist degree obviously is superior to the calcium stearate Zn composite heat stabilizer a little less than toxilic acid list dihydroxyphenyl propane ester rare earth.
Claims (9)
1. a stablizer that is used for processing PVC transparent sheet is characterized in that, described stablizer is by [R
2-OOC-R
1-COO
-]
2Ca
2+[R
2-OOC-R
1-COO
-]
2Zn
2+Form;
[R
2-OOC-R
1-COO
-]
2Ca
2+[R
2-OOC-R
1-COO
-]
2Zn
2+Mol ratio be 1: 1.2～2.5;
R wherein
1Be C
4～C
15Alkylidene group or C
2～C
14Alkenylene; R
2Be C
4～C
14Alkyl; And R
1And R
2The total number of carbon atoms be 8～24.
2. the stablizer that is used for processing PVC transparent sheet as claimed in claim 1 is characterized in that: R
1Be C
4, C
6Or C
10～C
15Alkylidene group or C
2～C
14Alkenylene; R
2Be C
4, C
5, C
6Or C
8～C
14Alkyl; And R
1And R
2The total number of carbon atoms be 8～24.
3. like each described stablizer that is used for processing PVC transparent sheet of claim 1～2, it is characterized in that described [R
2-OOC-R
1-COO
-]
2Ca
2+[R
2-OOC-R
1-COO
-]
2Zn
2+Mol ratio be 1: 1.5.
4. like each described preparation method who is used for the stablizer of processing PVC transparent sheet of claim 1～3, it is characterized in that, comprise
R
2-OH and HOOC-R
1-COOH carries out esterification and generates R under catalyst action
2-OOC-R
1The step of-COOH;
R
2-OOC-R
1-COOH carries out calcium zinc impregnation reaction and generates [R
2-OOC-R
1-COO
-]
2Ca
2+[R
2-OOC-R
1-COO
-]
2Zn
2+Step.
5. preparation method as claimed in claim 4 is characterized in that, the quality of described catalyzer is R
20.5～2% of-OH quality.
6. like claim 4 or 5 described preparing methods, it is characterized in that: HOOC-R
1-COOH and R
2The mol ratio of-OH is 1: 1～1.05.
7. preparation method as claimed in claim 6 is characterized in that, the temperature of described esterification is 115～150 ℃.
8. like each described application that is used for the stablizer of processing PVC transparent sheet at processing PVC transparent sheet of claim 1～3, the addition of described stablizer is 1～3% of a PVC quality.
9. a PVC clear sheet contains just like each described stablizer that is used for processing PVC transparent sheet of claim 1～3, transmittance>=90% of described PVC clear sheet when thickness 0.11-0.30mm, mist degree≤6.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101571150A CN101724210B (en) | 2009-12-22 | 2009-12-22 | Stabilizing agent for processing PVC transparent sheet and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101571150A CN101724210B (en) | 2009-12-22 | 2009-12-22 | Stabilizing agent for processing PVC transparent sheet and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101724210A CN101724210A (en) | 2010-06-09 |
| CN101724210B true CN101724210B (en) | 2012-05-23 |
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ID=42445805
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| CN105936679B (en) * | 2016-06-16 | 2019-03-01 | 浙江海普顿新材料股份有限公司 | A kind of maleic acid list polyvinyl alcohol ester barium salt and its application in PVC heat stabilizer |
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