CN105111635A - Application of pentaerythritol ester in PVC (polyvinyl chloride) blending modification - Google Patents
Application of pentaerythritol ester in PVC (polyvinyl chloride) blending modification Download PDFInfo
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- CN105111635A CN105111635A CN201510649442.3A CN201510649442A CN105111635A CN 105111635 A CN105111635 A CN 105111635A CN 201510649442 A CN201510649442 A CN 201510649442A CN 105111635 A CN105111635 A CN 105111635A
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Abstract
The invention relates to an application of pentaerythritol ester in PVC (polyvinyl chloride) blending modification. According to the application, carbon fibers are hydrolyzed with waste polyacrylonitrile precursor fibers, large quantity of carboxylic groups and small quantity of amide groups in hydrolysate are used comprehensively, the carboxylic groups and pentaerythritol have an esterification reaction, the pentaerythritol ester is prepared and taken as a stabilizing additive in PVC, the waste fibers are ground into nanoparticles to serve as a filler for PVC blending, with use of the stabilizing agent and the filler, the compatibility and the stability of the pentaerythritol ester in PVC blending are improved, undesirable phenomena in a PVC product production process are reduced greatly, sustainable utilization of resources is realized, the application field of the waste fibers is expanded, waste is changed into wealth, and the production cost is reduced greatly.
Description
Technical field
The invention belongs to the application of a kind of pentaerythritol ester in PVC blending and modifying.
Background technology
Along with the proposition of Green Chemistry, in PVC (polyvinyl chloride) blended formula, the consumption of the Pb stabilizer such as three salt, disalt sharply reduces, fatty acid stablizer becomes substitute, and especially fatty acid calcium zinc composite stabilizer becomes the main flow in stablizer with the performance of its excellence.But the soap class stablizers such as calcium zinc exist the phenomenon of " zinc burning ", this turns to co-stabilizer with regard to making people the sight of research.Tetramethylolmethane be a kind of PVC blended in important auxiliary agent, it and calcium zinc stabilizer are also by the phenomenon obviously can improving " zinc burns ", but owing to there is more hydroxyl in tetramethylolmethane, make its water absorbability stronger, thus make the compatibility of tetramethylolmethane and polyvinyl chloride resin poor, and easily make goods produce bubble, this also just limits the use of tetramethylolmethane.
The main method of current improvement is all tetramethylolmethane and micromolecular acid compounds are reacted, and prepares pentaerythritol ester, this kind of method overcome the above problems of can yet be regarded as, but rare people studies tetramethylolmethane and polymer acid compounds reacts.By utilizing polymer unit characteristics, improving gamma value, thus improving tetramethylolmethane compatibility, improving its stabilizing effect, and by macromolecule group feature, improve the plasticity in product molding process and oilness.
Acrylic fibers, in suitability for industrialized production, inevitably have the generation of waste silk, and the useless acrylic fibres total amount that current China produces every year, at about 100,000 tons, if do not reclaimed, will inevitably bring the waste of resource and the pollution of environment.Therefore strengthen the comprehensive utilization to polyacrylonitrile fibril for carbon fiber waste silk, realize the sustainable use of resource, there is vast potential for future development.The hydrolysis of polyacrylonitrile fibril for carbon fiber waste silk is mainly obtained polyacrylic acid or polyacrylamide by the existing report to polyacrylonitrile fibril for carbon fiber waste silk at present, for the preparation of high performance absorbent resin, flocculation agent, phase change material etc., but rarely have waste silk is applied to the blended middle use of PVC.
Summary of the invention
Invention broadly provides a kind of PVC blending modification method saving production cost.
The object of the present invention is to provide the application of a kind of pentaerythritol ester in PVC blending and modifying, the step of described PVC blending and modifying is as follows:
(1) by polyacrylonitrile fibril for carbon fiber waste silk sodium hydroxide lye in be hydrolyzed, by salt acid for adjusting pH to 6 ~ 7, with alcohol settling, obtain hydrolysate.
(2) the described hydrolysate obtained in tetramethylolmethane and step (1) is dropped in reactor, heating reflux reaction in a solvent, and after filtration, extracted with diethyl ether is separated, vacuum-drying obtains faint yellow product, obtains pentaerythritol ester.
(3) by high-precision intelligent ball mill grinding, polyacrylonitrile fibril for carbon fiber waste silk is prepared into nano level powder.
(4) by plasticizing forming after PVC, DOP, weighting agent, calcium-zinc composite stabilizing agent, pentaerythritol ester mixing.
Preferably, in step (1), temperature of reaction is 100 ~ 150 DEG C, and the solubility of sodium hydroxide lye is 10% ~ 25%.
Preferably, described in step (1), the molar ratio of polyacrylonitrile fibril for carbon fiber waste silk and sodium hydroxide lye is 1:0.2 ~ 1:1.2.
Preferably, described in step (1), hydrolysis time is 10 ~ 15h.
Preferably, the mol ratio 1.0:1 ~ 2.0:1 of described tetramethylolmethane and the middle described hydrolysate obtained of step (2).
Preferably, described in step (2), solvent is N-Methyl pyrrolidone.
Preferably, in step (2), Heating temperature is 200 ~ 280 DEG C, and the reaction times is 7 ~ 15h.
Preferably, described in step (4), PVC is 90 ~ 120 parts, and DOP is 0 ~ 10 part, and weighting agent is 8 to 15 parts, calcium-zinc composite stabilizing agent is 0.5 ~ 4.5 part, pentaerythritol ester 0.2 ~ 1 part.
Preferably, described in step (3), the granularity of weighting agent is 1 ~ 100nm.
Preferably, step (4) temperature of reaction is 180 ~ 220 DEG C.
The present invention has the following advantages: the present invention is by being hydrolyzed polyacrylonitrile fibril for carbon fiber waste silk, a large amount of hydroxy-acid group in comprehensive utilization hydrolysate and a small amount of amide group, hydroxy-acid group and tetramethylolmethane esterification are reacted, prepares pentaerythritol ester, as the stabilization aid in PVC.And by waste silk being ground to form nano particle as the blended weighting agent of PVC, the use of this stablizer and weighting agent, improve its consistency in PVC is blended and stability, greatly reduce the bad phenomenon in PVC product production process, achieve the sustainable use of resource, extend the Application Areas of waste silk, turn waste into wealth, greatly reduce production cost.
Accompanying drawing explanation
Fig. 1 is PVC blending and modifying static heat stability figure.
Fig. 2 is PVC blending and modifying dynamic thermal stability figure.
Embodiment
Set forth the present invention further below by way of specific embodiment, but be not limited to following embodiment.
One, specific embodiment
Embodiment 1
PVC blending modification method comprises the following steps:
(1) at 100 DEG C, by polyacrylonitrile fibril for carbon fiber waste silk, in the sodium hydroxide lye of 10%, (molar ratio of polyacrylonitrile fibril for carbon fiber waste silk and sodium hydroxide lye is 1:0.2) is hydrolyzed 10h, by salt acid for adjusting pH to 7, with alcohol settling, obtain hydrolysate.
(2) tetramethylolmethane and pulp water hydrolysis products (mol ratio 1.3:1) are dropped in reactor, in solvent, 200 DEG C of back flow reaction 7h are being heated using N-Methyl pyrrolidone, and after filtration, extracted with diethyl ether is separated, vacuum-drying obtains faint yellow product, obtains pentaerythritol ester.
(3) by high-precision intelligent ball mill grinding, polyacrylonitrile fibril for carbon fiber waste silk is prepared into nano level powder, granularity is 1nm, obtains weighting agent.
(4) by 100 parts of PVC, 10 parts of DOP (dibutyl ester), 10 parts of weighting agents, calcium-zinc composite stabilizing agents 3 parts, pentaerythritol ester 1 part mixing, at 180 DEG C of plasticizing formings.
Plasticizing product is 60min not zinc burning at 180 DEG C, and have good thermal stability, ageing-resistant performance is very high.
Embodiment 2
PVC blending modification method comprises the following steps:
(1) at 120 DEG C, polyacrylonitrile fibril for carbon fiber waste silk is hydrolyzed 12h in the sodium hydroxide lye (molar ratio of polyacrylonitrile fibril for carbon fiber waste silk and sodium hydroxide lye is 1:0.7) of 18%, by salt acid for adjusting pH to 6, with alcohol settling, obtain hydrolysate.
(2) tetramethylolmethane and pulp water hydrolysis products (mol ratio 1.0:1) are dropped in reactor, in solvent, 240 DEG C of back flow reaction 9h are being heated using N-Methyl pyrrolidone, and after filtration, extracted with diethyl ether is separated, vacuum-drying obtains faint yellow product, obtains pentaerythritol ester.
(3) by high-precision intelligent ball mill grinding, polyacrylonitrile fibril for carbon fiber waste silk is prepared into nano level powder, granularity is 30nm, obtains weighting agent.
(4) by 90 parts of PVC, 5 parts of DOP (dibutyl ester), 8 parts of weighting agents, calcium-zinc composite stabilizing agents 0.5 part, pentaerythritol ester 0.5 part mixing, at 220 DEG C of plasticizing formings.
Plasticizing product is 60min not zinc burning at 180 DEG C, and have good thermal stability, ageing-resistant performance is very high.
Embodiment 3
PVC blending modification method comprises the following steps:
(1) at 150 DEG C, by polyacrylonitrile fibril for carbon fiber waste silk, in the sodium hydroxide lye of 25%, (molar ratio of polyacrylonitrile fibril for carbon fiber waste silk and sodium hydroxide lye is 1:1) is hydrolyzed 15h, by salt acid for adjusting pH to 7, with alcohol settling, obtain hydrolysate.
(2) tetramethylolmethane and pulp water hydrolysis products (mol ratio 2.0:1) are dropped in reactor, in solvent, 280 DEG C of back flow reaction 12h are being heated using N-Methyl pyrrolidone, and after filtration, extracted with diethyl ether is separated, vacuum-drying obtains faint yellow product, obtains pentaerythritol ester.
(3) by high-precision intelligent ball mill grinding, polyacrylonitrile fibril for carbon fiber waste silk is prepared into nano level powder, granularity is 100nm, obtains weighting agent.
(4) by 120 parts of PVC, 8 parts of DOP (dibutyl ester), 12 parts of weighting agents, calcium-zinc composite stabilizing agents 4.5 parts, pentaerythritol ester 0.4 part mixing, at 200 DEG C of plasticizing formings.
Plasticizing product is 60min not zinc burning at 180 DEG C, and have good thermal stability, ageing-resistant performance is very high.
Embodiment 4
PVC blending modification method comprises the following steps:
(1) at 110 DEG C, by polyacrylonitrile fibril for carbon fiber waste silk, in the sodium hydroxide lye of 12%, (molar ratio of polyacrylonitrile fibril for carbon fiber waste silk and sodium hydroxide lye is 1:1.2) is hydrolyzed 10h, by salt acid for adjusting pH to 7, with alcohol settling, obtain hydrolysate.
(2) tetramethylolmethane and pulp water hydrolysis products (mol ratio 1.5:1) are dropped in reactor, in solvent, 220 DEG C of back flow reaction 15h are being heated using N-Methyl pyrrolidone, and after filtration, extracted with diethyl ether is separated, vacuum-drying obtains faint yellow product, obtains pentaerythritol ester.
(3) by high-precision intelligent ball mill grinding, polyacrylonitrile fibril for carbon fiber waste silk is prepared into nano level powder, granularity is 80nm, obtains weighting agent.
(4) by 55 parts of PVC, 15 parts of weighting agents, calcium-zinc composite stabilizing agents 1.6 parts, pentaerythritol ester 0.2 part mixing, at 210 DEG C of plasticizing formings.
Plasticizing product is 60min not zinc burning at 180 DEG C, and have good thermal stability, ageing-resistant performance is very high.
Two, performance test
Senile experiment
By the plasticizing product 8 parts of embodiment 1 gained under 180 DEG C of conditions at 10min, 20min, 30min, 40min, 50min, 60min, 70min, during 80min, sampling is observed, as shown in Figure 1, until zinc just occurs 80min burn phenomenon, zinc burns time lengthening, illustrate that plasticizing product has good thermostability, ageing-resistant performance is high.
Rheological experiment
At 180 DEG C, mixture in the step (4) in embodiment 2 is plastified in torque rheometer, obtain torque curve, as shown in Figure 2, illustrate that this ester class co-stabilizer can obviously reduce plasticizing moment of torsion, reduce fusion time, having good self lubricity, is a kind of desirable co-stabilizer.
The present invention is by being hydrolyzed polyacrylonitrile fibril for carbon fiber waste silk, and a large amount of hydroxy-acid group in comprehensive utilization hydrolysate and a small amount of amide group, react hydroxy-acid group and tetramethylolmethane esterification, prepare pentaerythritol ester, as the stabilization aid in PVC.And by waste silk being ground to form nano particle as the blended weighting agent of PVC, the use of this stablizer and weighting agent, improve its consistency in PVC is blended and stability, greatly reduce the bad phenomenon in PVC product production process, achieve the sustainable use of resource, extend the Application Areas of waste silk, turn waste into wealth, greatly reduce production cost.
To one skilled in the art, according to technical scheme described above and design, other various corresponding change and deformation can be made, and all these change and deformation all should belong within the protection domain of the claims in the present invention.
Claims (10)
1. the application of pentaerythritol ester in PVC blending and modifying, its step is as follows:
(1) by polyacrylonitrile fibril for carbon fiber waste silk sodium hydroxide lye in be hydrolyzed, by salt acid for adjusting pH to 6 ~ 7, with alcohol settling, obtain hydrolysate.
(2) the described hydrolysate obtained in tetramethylolmethane and step (1) is dropped in reactor, heating reflux reaction in a solvent, and after filtration, extracted with diethyl ether is separated, vacuum-drying obtains faint yellow product, obtains pentaerythritol ester.
(3) by high-precision intelligent ball mill grinding, polyacrylonitrile fibril for carbon fiber waste silk is prepared into nano level powder.
(4) by plasticizing forming after PVC, DOP, weighting agent, calcium-zinc composite stabilizing agent, pentaerythritol ester mixing.
2. the application of pentaerythritol ester according to claim 1 in PVC blending and modifying, is characterized in that: in step (1), temperature of reaction is 100 ~ 150 DEG C, and the solubility of sodium hydroxide lye is 10% ~ 25%.
3. the application of pentaerythritol ester according to claim 1 and 2 in PVC blending and modifying, is characterized in that: described in step (1), the molar ratio of polyacrylonitrile fibril for carbon fiber waste silk and sodium hydroxide lye is 1:0.2 ~ 1:1.2.
4. the application of pentaerythritol ester according to claim 1 in PVC blending and modifying, is characterized in that: described in step (1), hydrolysis time is 10 ~ 15h.
5. the application of pentaerythritol ester according to claim 1 in PVC blending and modifying, is characterized in that: the mol ratio 1.0:1 ~ 2.0:1 of described tetramethylolmethane and the middle described hydrolysate obtained of step (2).
6. the application of pentaerythritol ester according to claim 1 in PVC blending and modifying, is characterized in that: described in step (2), solvent is N-Methyl pyrrolidone.
7. the application of pentaerythritol ester according to claim 1 in PVC blending and modifying, is characterized in that: in step (2), Heating temperature is 200 ~ 280 DEG C, and the reaction times is 7 ~ 15h.
8. the application of pentaerythritol ester according to claim 1 in PVC blending and modifying, it is characterized in that: described in step (4), PVC is 90 ~ 120 parts, DOP is 0 ~ 10 part, and weighting agent is 8 to 15 parts, calcium-zinc composite stabilizing agent is 0.5 ~ 4.5 part, pentaerythritol ester 0.2 ~ 1 part.
9. the application of pentaerythritol ester according to claim 1 in PVC blending and modifying, is characterized in that: described in step (3), the granularity of weighting agent is 1 ~ 100nm.
10. the application of pentaerythritol ester according to claim 1 in PVC blending and modifying, is characterized in that: step (4) temperature of reaction is 180 ~ 220 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1760258A (en) * | 2005-11-04 | 2006-04-19 | 常熟市中联光电新材料有限责任公司 | Flexible vinyl dedicated to wire and cable |
| CN1847304A (en) * | 2005-04-15 | 2006-10-18 | 江苏圣安电缆有限公司 | Environment friendly soft PVC plastic without heavy metal for electric wire and cable |
| CN1931915A (en) * | 2005-09-16 | 2007-03-21 | 无锡江南电缆有限公司 | Soft PVC plastic for electric wire and cable |
| US20100292379A1 (en) * | 2009-05-12 | 2010-11-18 | Nan Ya Plastics Corporation | PVC resin composition and products made of the same |
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2015
- 2015-10-09 CN CN201510649442.3A patent/CN105111635A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847304A (en) * | 2005-04-15 | 2006-10-18 | 江苏圣安电缆有限公司 | Environment friendly soft PVC plastic without heavy metal for electric wire and cable |
| CN1931915A (en) * | 2005-09-16 | 2007-03-21 | 无锡江南电缆有限公司 | Soft PVC plastic for electric wire and cable |
| CN1760258A (en) * | 2005-11-04 | 2006-04-19 | 常熟市中联光电新材料有限责任公司 | Flexible vinyl dedicated to wire and cable |
| US20100292379A1 (en) * | 2009-05-12 | 2010-11-18 | Nan Ya Plastics Corporation | PVC resin composition and products made of the same |
Non-Patent Citations (1)
| Title |
|---|
| 刘栋 等: "PAN原丝废丝制备新型季戊四醇酯及其应用", 《高科技纤维与应用》 * |
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