CN100425426C - Processing method for partially untangled polyningl chloride master batch at 10-120deg.c range - Google Patents
Processing method for partially untangled polyningl chloride master batch at 10-120deg.c range Download PDFInfo
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- CN100425426C CN100425426C CNB2006100883927A CN200610088392A CN100425426C CN 100425426 C CN100425426 C CN 100425426C CN B2006100883927 A CNB2006100883927 A CN B2006100883927A CN 200610088392 A CN200610088392 A CN 200610088392A CN 100425426 C CN100425426 C CN 100425426C
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- polyvinyl chloride
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Abstract
The present invention is dissolving and depositing process of preparing partially untangled polyvinyl chloride master batch at 10-120deg.c, and belongs to the field of polyvinyl chloride processing technique. Polyvinyl chloride is first dissolved in tetrahydrofuran or bis (2-ethylhexyl) phthalate through stirring to obtain homogeneous solution, the solution is poured into ethanol or methanol to produce precipitate, and the precipitate is washed with ethanol or methanol and dried to obtain powdered partially untangled polyvinyl chloride master batch. The powdered partially untangled polyvinyl chloride master batch is applied with pressure of 5-300 MPa at 10-120deg.c for 1 min to 1 hr to obtain the product with physical and mechanical performance the same as that of product that convenient heat processing method.
Description
One, technical field:
The present invention relates to part disentanglement chloride master batch processing method in 10 ℃ to 120 ℃ scopes, belong to polyvinyl chloride technology field.
Two, background technology:
Polyvinyl chloride is a kind of high comprehensive performance, broad-spectrum resins for universal use.Polyvinyl chloride has abundant raw material, manufacturing process maturation, outstanding feature such as cheap, of many uses, can process by modes such as mold pressing, laminated, injection moulding, extrusion molding, calendering, blowing hollows.But because its hear resistance is relatively poor, begin to decompose variable color in 130 ℃-140 ℃, separate out HCI, make properties of product descend, and corrosion processing equipment easily.
High polymerization degree and superelevation degree of polymerization polyvinyl chloride with respect to the ordinary soft polyvinyl chloride have under little, the high temperature of compression permanent deformation that dimensional stability is good, characteristics such as hardness good stability when good heat resistance, change temperature, oil resistant solvent resistance are good, ageing-resistant performance and mechanical performance excellence.But high polymerization degree and the physical entanglement under molten condition of superelevation degree of polymerization polyvinyl chloride sharply increase, and cause the flowability in the process poor.Therefore during the commercial Application of high polymerization degree and superelevation degree of polymerization polyvinyl chloride, the degree of polymerization is limited in 2500.More the extensive use of the polyvinyl chloride of high polymerization degree is seriously restricted.
At present the processing temperature of polyvinyl chloride boardy product (sheet material, profile shapes, tubing etc.) is at 180 ℃ more than-200 ℃, even and the soft goods of polyvinyl chloride especially the polyvinyl chloride soft goods of HMW in process, add a large amount of plasticizer also will be 140 ℃ of processing more than-150 ℃.These processing temperatures have all surpassed 130 ℃-140 ℃ of the heat decomposition temperatures of polyvinyl chloride.And the use of a large amount of plasticizer has also aggravated the global environment pollution.Also have and in high polymerization degree and superelevation degree of polymerization polyvinyl chloride, add the flowability that 0-15 part polyvinyl-chloride of low-polymerization degree improves processing.The shortcoming of doing like this is to make that actual molecular weight reduces, and molecular weight distribution is widened, and the mechanical property of corresponding articles is also good not as what expect.{ list of references [1] Si Qinda comes, Hua Youqing China plastics, 1994, Vol.8, No.1, pp.37-42[2] Liu Fang, open army's specific rubber goods, 2000, Vol.21, No.3, pp.11-14[3] Liu Yu strong elasticity body 2000, Vol.10, No.2, pp.48-51[4] Liu Ling plum China chlor-alkali 2000, No.7, pp.24-25[5] R.N.Haward, R.J.Young The Physics ofGlassyPolymers 1997,2nd edn.pp.20-22[6] Chinese patent: ZL03131504.6}
Three, summary of the invention
The objective of the invention is: processing part disentanglement chloride master batch in 10 ℃ to 120 ℃ scopes solves the technical barrier that polyvinyl chloride is easy to decompose in the existing polyvinyl chloride processing method.
The object of the present invention is achieved like this:
Polyvinyl chloride is dissolved in oxolane or phthalic acid two (the 2-ethyl the is own) ester by 0.1-50wt%, is stirred well to the solution transparent and homogeneous.Solution poured in ethanol or the methyl alcohol precipitate, and with ethanol or methanol wash precipitation, drying obtains Powdered part disentanglement chloride master batch.The chloride master batch of Powdered part disentanglement added in the mould uniformly paves, mould is placed on forcing press or the compression molding instrument, at normal temperature to being lower than in the polyvinyl chloride decomposition temperature scope pressure that (10 ℃ to 120 ℃ scope in) apply 5-300MPa.And pressure was kept 1 minute to 1 hour.During withstanding pressure, the polyvinyl chloride strand has slippage by a relatively large margin, promptly shows the certain fluidity energy.Can obtain after release, the demoulding and polrvinyl chloride product that conventional hot-working sample has the same physical mechanical performance.Following table is the performance table of comparisons of the polrvinyl chloride product (molecular weight is 150,000) that makes of this processing method and conventional processing method.Because this processing method is to carry out below the heat decomposition temperature of polyvinyl chloride, has solved the difficult problem of polyvinyl chloride thermal degradation in the conventional process.
The polrvinyl chloride product performance table of comparisons that this processing method and conventional processing method make
| The polrvinyl chloride product that this processing method makes | The polrvinyl chloride product that conventional processing method makes | |
| The transparency | Clear, colorless | Transparent jaundice |
| Hot strength (MPa) | 12.6 | 12.9 |
| The % elongation at break | 359 | 355 |
| Young's modulus A(Pa) | 2×10 9 | 2×10 9 |
| Whether degrade B | Not | Be |
| Whether add plasticizer | Not | Be |
| Whether add antioxidant | Not | Be |
A tests from DMTA
B is from the RAMAN spectrum test
The advantage of processing method of the present invention is:
1. less energy intensive in the forming process: this method adopts lower processing temperature (in 10 ℃ to the 120 ℃ scopes), makes less energy intensive in the forming process.
2. polyvinyl chloride is not degraded in the extrusion forming process repeatedly: because the processing temperature of this method is lower than the heat decomposition temperature of polyvinyl chloride, avoided the problem of thermal degradation in the conventional polyvinyl chloride process, also with regard to problems such as the reduction of having avoided properties of product and equipment corrosions.
3. need not to add plasticizer: this method processing polyvinyl chloride can not add plasticizer.In the polyvinyl chloride process, reduce plasticizer dosage, not only can reduce cost, improve the rigidity of goods, can also reduce the pollution of plasticizer environment.
4. need not to add antioxidant: because there is not thermal degradation problems in this method processing polyvinyl chloride, can not add antioxidant in the chloride master batch, antioxidant is to the pollution of environment in the minimizing goods.
5. handle easy and simple to handle: the solvent that this method is used is industrialized chemical products, and can recycle, and treatment process is simple, and its corresponding operating cost is lower.
6. has the same physical mechanical performance with conventional hot-working goods: adopt the polrvinyl chloride product of this method preparation and the polrvinyl chloride product of conventional hot-working method preparation to have identical physical and mechanical properties.
Purposes of the present invention: on method, the processing technology of polyvinyl chloride is reformed, Powdered part disentanglement chloride master batch through obtaining behind the dissolution precipitation at normal temperature to being lower than in the polyvinyl chloride pyrolysis temperature range (10 ℃ to 120 ℃ scopes) processing, product has good physical and mechanical properties, reduced environmental pollution and equipment corrosion simultaneously, be expected to be applied to polyvinyl chloride and blend thereof (as with the blend of acrylonitrile-butadiene rubber, ABS engineering resin etc.) and the large-scale industrial production of polyvinyl chloride composite materials.
Four, specific implementation method of the present invention:
Example 1, polyvinyl chloride are 10 ℃ of processing:
Polyvinyl chloride (molecular weight is 80,000) 100 grams are joined 200-10, and in 000 gram oxolane (THF) solvent, the concentration of solution is 1-50wt%, is transparent and homogeneous in normal-temperature dissolution, the system of being stirred to.Solution is poured in ethanol or the methyl alcohol and is settled out polyvinyl chloride, and with ethanol or methanol wash, drying obtains Powdered part disentanglement chloride master batch.The chloride master batch of this Powdered part disentanglement is added in the mould tiling evenly, be placed on mould on the conventional press or 10 ℃ of pressure that applies 250MPa 30 minutes on the compression molding instrument, obtain transparent sample fully.Sample has identical Young's modulus (2 * 10 through the sample of DMTA test shows and conventional hot-working method preparation
9Pa).Sample is not found because 1117cm appears in thermal degradation by the RAMAN analytical test
-1And 1497cm
-1The conjugated double bond peak.And tangible conjugated double bond peak appears on its RAMAN spectrogram of sample of conventional processing, illustrate that sample through conventional processing thermal degradation has taken place.
Example 2, polyvinyl chloride are 60 ℃ of processing:
Polyvinyl chloride (molecular weight is 223,000) 100 grams are joined 500-10, and in the 000 gram dioctyl phthalate solvent, the concentration of solution is 1-20wt%, is transparent and homogeneous 80 ℃ of dissolvings, the systems of being stirred to.Solution is poured in ethanol or the methyl alcohol and is settled out polyvinyl chloride, and with ethanol or methanol wash, drying obtains Powdered part disentanglement chloride master batch.The chloride master batch of this Powdered part disentanglement is added in the mould tiling evenly, be placed on mould on the conventional press or 60 ℃ of pressure that applies 100MPa 5 minutes on the compression molding instrument, obtain transparent sample fully.Sample has identical Young's modulus (2 * 10 through the sample of DMTA test shows and conventional hot-working method preparation
9Pa).Sample is not found because 1117cm appears in thermal degradation by the RAMAN analytical test
-1And 1497cm
-1The conjugated double bond peak.And tangible conjugated double bond peak appears on its RAMAN spectrogram of sample of conventional processing, illustrate that sample through conventional processing thermal degradation has taken place.
The processing of 3,120 ℃ of polyvinyl chloride of example:
Polyvinyl chloride (molecular weight is 300,000) 100 grams are joined 500-10, and in the 000 gram dioctyl phthalate solvent, the concentration of solution is 1-20wt%, is transparent and homogeneous 80 ℃ of dissolvings, the systems of being stirred to.Solution is poured in ethanol or the methyl alcohol and is settled out polyvinyl chloride, and with ethanol or methanol wash, drying obtains Powdered part disentanglement chloride master batch.The chloride master batch of this Powdered part disentanglement is added in the mould tiling evenly, be placed on mould on the conventional press or 120 ℃ of pressure that applies 100MPa 1 minute on the compression molding instrument, obtain transparent sample fully.Sample has identical Young's modulus (2 * 10 through the sample of DMTA test shows and conventional hot-working method preparation
9Pa).Sample is not found because 1117cm appears in thermal degradation by the RAMAN analytical test
-1And 1497cm
-1The conjugated double bond peak.And tangible conjugated double bond peak appears on its RAMAN spectrogram of sample of conventional processing, illustrate that sample through conventional processing thermal degradation has taken place.
The processing of 4,60 ℃ of polyvinyl chloride composite materials of example:
Polyvinyl chloride (molecular weight is 60,000) 100 grams are joined 500-10, and in 000 gram oxolane (THF) solvent, the concentration of solution is 1-50wt%, is transparent and homogeneous in normal-temperature dissolution, the system of being stirred to.Solution is poured in ethanol or the methyl alcohol and is settled out polyvinyl chloride, and with ethanol or methanol wash, adds 4～6 parts of calcium carbonate (CaCO then in the suspension of the ethanol of polyvinyl chloride or methyl alcohol
3), 8～10 parts of haloflexes (CPE) and 1～2 part of impact modifier FM-21, filtration, drying promptly obtain Powdered polyvinyl chloride composite after stirring.Should be Powdered polyvinyl chloride composite add in the mould tiling evenly, be placed on mould on the conventional press or 60 ℃ of pressure that applies 250MPa 10 minutes on the compression molding instrument, obtain transparent sample fully.Sample is tested through DMTA, finds to have identical Young's modulus (2 * 10 with the polyvinyl chloride sample of conventional hot-working method preparation
9Pa).
Claims (3)
1, part disentanglement chloride master batch is processing method in 10 ℃ to 120 ℃ scopes, polyvinyl chloride is dissolved in oxolane or phthalic acid two (the 2-ethyl the is own) ester, be stirred well to the solution transparent and homogeneous, uniform solution poured in ethanol or the methyl alcohol be settled out polyvinyl chloride, and with ethanol or methanol wash precipitation, dry, obtain Powdered part disentanglement chloride master batch, it is characterized in that: Powdered part disentanglement chloride master batch tiles in the mould, unidirectionally on 10 ℃ to 120 ℃ scope intrinsic pressure machines or compression molding instrument applied 5-300MPa pressure 1 minute-1 hour, obtain and the identical clear sheet of conventional hot-working method physical and mechanical properties.
2, according to the described part disentanglement of claim 1 chloride master batch processing method in 10 ℃ to 120 ℃ scopes, its feature is that also the molecular weight ranges of polyvinyl chloride is 50,000～500,000.
3, according to the described part disentanglement of claim 1 chloride master batch processing method in 10 ℃ to 120 ℃ scopes, its feature is that also the concentration of the solution that polyvinyl chloride and oxolane or phthalic acid two (the 2-ethyl is own) ester are made into is 1-50wt%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100883927A CN100425426C (en) | 2006-07-17 | 2006-07-17 | Processing method for partially untangled polyningl chloride master batch at 10-120deg.c range |
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| CNB2006100883927A CN100425426C (en) | 2006-07-17 | 2006-07-17 | Processing method for partially untangled polyningl chloride master batch at 10-120deg.c range |
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| CN100425426C true CN100425426C (en) | 2008-10-15 |
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| CN116217964A (en) * | 2022-11-25 | 2023-06-06 | 北京科技大学 | Method for preparing low-dispersion index high-molecular weight polyvinyl chloride by centrifugal separation technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1399587A (en) * | 1999-06-15 | 2003-02-26 | 让-皮埃尔·伊巴尔 | Plastics viscosity control method and apparatus |
| CN1477142A (en) * | 2003-05-20 | 2004-02-25 | 南京大学 | Preparation method of polyvinyl chloride disentanglement mother material with high polymerization degree and ultrahigh polymerization degree |
| CN1602241A (en) * | 2001-10-12 | 2005-03-30 | 斯蒂茨丁荷兰聚合物学会 | Process to sinter ultra high molecular weight polyethylene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1399587A (en) * | 1999-06-15 | 2003-02-26 | 让-皮埃尔·伊巴尔 | Plastics viscosity control method and apparatus |
| CN1602241A (en) * | 2001-10-12 | 2005-03-30 | 斯蒂茨丁荷兰聚合物学会 | Process to sinter ultra high molecular weight polyethylene |
| CN1477142A (en) * | 2003-05-20 | 2004-02-25 | 南京大学 | Preparation method of polyvinyl chloride disentanglement mother material with high polymerization degree and ultrahigh polymerization degree |
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Effective date of registration: 20070427 Address after: 210093 No. 22, Hankou Road, Nanjing, Jiangsu Applicant after: Nanjing University Co-applicant after: Changzhou Ding Ding Engineering Plastics Co., Ltd. Address before: 210093 No. 22, Hankou Road, Nanjing, Jiangsu Applicant before: Nanjing University Co-applicant before: Runtec Chemical Co., Ltd. |
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Effective date of registration: 20081128 Address after: No. 22, Hankou Road, Jiangsu, Nanjing Province, China: 210093 Co-patentee after: Runtec Chemical Co., Ltd. Patentee after: Nanjing University Address before: No. 22, Hankou Road, Jiangsu, Nanjing Province, China: 210093 Co-patentee before: Changzhou Ding Ding Engineering Plastics Co., Ltd. Patentee before: Nanjing University |
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Owner name: CHANGZHOU XUNTIAN ENERGY SAVING SCIENCE + TECHNOLO Free format text: FORMER OWNER: CHANGZHOU RUNTEC CHEMICAL CO., LTD. Effective date: 20141011 |
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