CN111825937A - Thermoplastic polyvinyl alcohol material and processing method thereof - Google Patents
Thermoplastic polyvinyl alcohol material and processing method thereof Download PDFInfo
- Publication number
- CN111825937A CN111825937A CN202010572549.3A CN202010572549A CN111825937A CN 111825937 A CN111825937 A CN 111825937A CN 202010572549 A CN202010572549 A CN 202010572549A CN 111825937 A CN111825937 A CN 111825937A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- thermoplastic
- screw extruder
- thermoplastic polyvinyl
- plasticizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 61
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 58
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 26
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000003672 processing method Methods 0.000 title claims abstract description 9
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 60
- 239000004014 plasticizer Substances 0.000 claims abstract description 16
- 238000010128 melt processing Methods 0.000 claims abstract description 9
- 239000008187 granular material Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000008188 pellet Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 abstract description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006136 alcoholysis reaction Methods 0.000 abstract description 6
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- YHOWYTOWCBNTHB-UHFFFAOYSA-N 4-benzoyloxybutyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCCCOC(=O)C1=CC=CC=C1 YHOWYTOWCBNTHB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010096 film blowing Methods 0.000 abstract description 2
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
Abstract
A thermoplastic polyvinyl alcohol material and a processing method thereof are disclosed, the polyvinyl alcohol material comprises the following components by mass fraction: 50-90 parts of polyvinyl alcohol; 10-40 parts of plasticizer. The polyvinyl alcohol is preferably multicomponent, the degree of polymerization is preferably 300-2400, and the degree of alcoholysis is preferably 70-99% by mole fraction. The plasticizer is preferably polytetrahydrofuran dibenzoate which is compounded with one or two of 1, 4-butanediol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate and glycerol. Adding two or more polyvinyl alcohols and a plasticizer into a double-screw extruder at the same time according to the required amount according to the proportion for melt processing to obtain the thermoplastic polyvinyl alcohol granules. According to the invention, one or more plasticizers are added into the PVA raw material, and the PVA material is obtained through one-step melt processing by a double-screw extruder, so that downstream customers can use the material produced by the method to produce multilayer composite films by adopting a film blowing method and other thermoplastic processing methods.
Description
Technical Field
The invention belongs to the field of chemical products, and particularly relates to a thermoplastic polyvinyl alcohol material and a processing method thereof.
Background
The hydroxyl structure on the molecular chain link of the polyvinyl alcohol endows the polyvinyl alcohol film with excellent gas barrier property, excellent performances of oil resistance, wear resistance, chemical corrosion resistance, tear resistance, static resistance, transparency and the like, and can be used for high-barrier packaging of food, seafood dry goods, rare traditional Chinese medicinal materials, tobacco and various spices. The polyvinyl alcohol has small amplitude and no edge curl when being melted and extruded, and can be used as a coating material for carton coating, tin foil coating, pipeline coating, film coating and the like for packaging milk, fruit juice and other liquids.
A large amount of hydroxyl groups in a polyvinyl alcohol molecular chain form intermolecular hydrogen bonds, the melting temperature (226 ℃) of the intermolecular hydrogen bonds is very close to the thermal decomposition temperature (200-250 ℃), and thermal decomposition occurs during melting, so that the thermoplastic processing and molding of the polyvinyl alcohol are limited. The preparation of the polyvinyl alcohol film can only adopt a solution forming method with complex process, low efficiency and high energy consumption at present. At present, the most promising modification method, which is most easily industrialized, is to add a small amount of additives to produce the melt-processable polyvinyl alcohol. The polyvinyl alcohol produced by adding the auxiliary agent has better fluidity and can meet the requirements of melt processing and forming such as blow molding, tape casting and the like.
Chinese patent CN201910600020.5 discloses a preparation method and application of an environment-friendly plasticizer for processing PVA films, wherein low molecular weight polytetrahydrofuran and benzoic acid are used as raw materials, the raw materials are placed in a flask, after being uniformly stirred, a catalyst and a water-carrying agent are added, reflux reaction is carried out for 3-7h at the temperature of 180-plus-210 ℃, the catalyst is extracted and filtered after the reaction is finished, and then the transparent or slightly yellow polytetrahydrofuran dibotron is obtained after sodium bicarbonate neutralization, water washing, reduced pressure distillation and decoloration. Distilled water and plasticizer are added into PVA, and the film is formed by twin-screw extrusion. The processing method is complex, and the PVA material processed by melting can not be obtained in one step.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a processing method for producing meltable PVA by mainly using a thermoplastic polyvinyl alcohol material.
The technical scheme adopted by the invention is as follows:
a melt-processable polyvinyl alcohol material comprises the following components in percentage by mass:
50-90 parts of polyvinyl alcohol; 10-40 parts of plasticizer.
The polyvinyl alcohol is preferably multicomponent, the degree of polymerization is preferably 300-2400, and the degree of alcoholysis is preferably 70-99% by mole fraction. The plasticizer is preferably polytetrahydrofuran dibenzoate which is compounded with one or two of 1, 4-butanediol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate and glycerol.
A processing method of a thermoplastic polyvinyl alcohol material comprises the following specific processing schemes: adding two or more polyvinyl alcohols and plasticizers into a double-screw extruder at the same time according to the required amount according to the proportion for melt processing to obtain the thermoplastic polyvinyl alcohol granules. In the technical scheme, the melt processing temperature of the double-screw extruder is preferably 120-240 ℃, and the screw rotating speed is preferably 80-300 rpm. Adding the thermoplastic polyvinyl alcohol granules into a single-screw extruder, and melting, extruding and blowing the granules to obtain the polyvinyl alcohol single-layer film. Adding the thermoplastic polyvinyl alcohol granules, the LDPE and the adhesive into a double-screw extruder, and melting, extruding and blowing the film to obtain the three-layer or five-layer composite film. The melt processing temperature of the double-screw extruder is preferably 140-220 ℃, the rotating speed of the middle layer screw is 10-120r/min, the rotating speed of the secondary outer layer screw is 10-120r/min, and the rotating speed of the outermost layer screw is 10-110 r/min.
The invention has the obvious effect that the PVA material is melt-processed by adding one or more polytetrahydrofuran dibenzoate plasticizers or composite plasticizers into the PVA raw material and performing one-step extrusion through a double-screw extruder. Downstream customers can use the material produced by the method to produce multilayer composite films by adopting the thermoplastic process such as a film blowing method and the like.
Detailed Description
The present invention is further illustrated by the following examples, which are provided only for the understanding of the present invention and are not intended to be limiting.
Example 1:
70 parts of polyvinyl alcohol material (with the polymerization degree of 1700 and the alcoholysis degree of 88%), 30 parts of plasticizer (with the polymerization degree of 1700 and the alcoholysis degree of 99%) and 10% of polytetrahydrofuran dibenzoate are simultaneously added into a double-screw extruder, the temperature of 1 section of the extruder is 150 ℃, the temperature of 2-13 sections of the extruder is 160 ℃, the rotating speed of a screw is 180rpm, and extruded sample strips are granulated by a granulator after being cooled to obtain the thermoplastic PVA granules. Of the PVA pellets obtained: tm:150 ℃, MFR: 4.5g/10min (2.16Kg, 200 ℃ C.), and a yellowness index of 8.
Example 2:
the thermoplastic processed PVA pellets prepared in example 1 were added to a single screw extruder at a temperature of 160 ℃ in section 1, 170 ℃ in section 2-13 and 180rpm in screw speed, and the PVA pellets were plasticized, melted, blown, conveyed and drawn by a roller and wound to obtain a PVA film. The thickness of the film was 15 μm, the breaking strength of the film was 50MPa, the elongation at break was 220%, and the value of the Yellowness Index (YI) of transparency was 0.8.
Example 3:
70 parts of polyvinyl alcohol material (with the polymerization degree of 1700 and the alcoholysis degree of 88%), 30 parts of plasticizer (with the polymerization degree of 1700 and the alcoholysis degree of 99%) and 10% of plasticizer (5% of polytetrahydrofuran dibenzoate and 5% of BDO dibenzoate) are simultaneously added into a double-screw extruder, the temperature of 1 section of the extruder is 170 ℃, the temperature of 2-13 sections of the extruder is 180 ℃, the rotating speed of a screw is 200rpm, and extruded sample strips are granulated by a granulator after being cooled to obtain thermoplastic processed PVA granules. Of the PVA pellets obtained: tm:160 ℃, MFR: 5g/10min (2.16Kg, 200 ℃ C.), and a yellowness index of 12.
Example 4:
the thermoplastic processed PVA pellets prepared in example 3 were added to a single screw extruder at a temperature of 190 ℃ in 1-4 stages, and the PVA pellets were plasticized, melted, blown, conveyed by rolls, drawn, and wound to obtain a PVA film. The thickness of the film was 15 μm, the breaking strength of the film was 40MPa, the elongation at break was 180%, and the value of the Yellowness Index (YI) of transparency was 1.2.
Example 5:
the thermoplastic processed PVA pellets prepared in the example 1 are added into a single-screw extruder, the temperature of 1-5 sections of the extruder is 190 ℃, and the PVA pellets, LDPE and adhesive are plasticized, melted, blown into a film, conveyed by a roller, stretched and rolled to obtain the PVA film. The film had a thickness of 45 μm, a tensile strength of 20MPa, an elongation of 300%, a value of the Yellowness Index (YI) of 0.8, and a haze of 8.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple changes or equivalent substitutions that can be made by those skilled in the art within the technical scope of the present invention are within the technical scope of the present invention.
Claims (6)
1. The thermoplastic polyvinyl alcohol material is characterized by comprising the following components in percentage by mass:
50-90 parts of polyvinyl alcohol; 10-40 parts of plasticizer.
2. The thermoplastic polyvinyl alcohol material as claimed in claim 1, wherein the polyvinyl alcohol is preferably multicomponent, the degree of polymerization is preferably 300-2400-.
3. The processing method of the thermoplastic polyvinyl alcohol material is characterized in that two or more polyvinyl alcohols and plasticizers with required amount are simultaneously added into a double-screw extruder according to the proportion to be subjected to melt processing to obtain thermoplastic polyvinyl alcohol granules.
4. The method for processing the thermoplastic polyvinyl alcohol material as claimed in claim 3, wherein the melt processing temperature of the twin-screw extruder is preferably 120-240 ℃, and the screw rotation speed is preferably 80-300 rpm.
5. The method as claimed in claim 3, wherein the thermoplastic polyvinyl alcohol material is prepared by melting, extruding and blowing a three-layer or five-layer composite film by feeding the thermoplastic polyvinyl alcohol pellets, LDPE and adhesive material into a twin-screw extruder.
6. The method for processing the thermoplastic polyvinyl alcohol material as claimed in claim 3, wherein the melt processing temperature of the twin-screw extruder is preferably 140 ℃ to 220 ℃, the screw rotation speed of the middle layer is 10r/min to 120r/min, the screw rotation speed of the second outer layer is 10r/min to 120r/min, and the screw rotation speed of the outermost layer is 10r/min to 110 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010572549.3A CN111825937A (en) | 2020-06-22 | 2020-06-22 | Thermoplastic polyvinyl alcohol material and processing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010572549.3A CN111825937A (en) | 2020-06-22 | 2020-06-22 | Thermoplastic polyvinyl alcohol material and processing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111825937A true CN111825937A (en) | 2020-10-27 |
Family
ID=72897858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010572549.3A Pending CN111825937A (en) | 2020-06-22 | 2020-06-22 | Thermoplastic polyvinyl alcohol material and processing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111825937A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105128414A (en) * | 2015-09-06 | 2015-12-09 | 崔跃飞 | Composite film material of embedded window structure and preparation method thereof |
| CN107936431A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Polyvinyl alcohol water solubility casting films and preparation method thereof |
| CN107936430A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | High fluidity polyvinyl alcohol that thermoplastification is modified, cast film materials and preparation method thereof |
| CN107987322A (en) * | 2017-12-21 | 2018-05-04 | 苏州星火丰盈环保包装有限公司 | A kind of preparation method of biodegradable mulch |
| CN110437501A (en) * | 2019-07-04 | 2019-11-12 | 中国石化长城能源化工（宁夏）有限公司 | A kind of preparation method and application for PVA film environment-friendly plasticizer |
-
2020
- 2020-06-22 CN CN202010572549.3A patent/CN111825937A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105128414A (en) * | 2015-09-06 | 2015-12-09 | 崔跃飞 | Composite film material of embedded window structure and preparation method thereof |
| CN107936431A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | Polyvinyl alcohol water solubility casting films and preparation method thereof |
| CN107936430A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | High fluidity polyvinyl alcohol that thermoplastification is modified, cast film materials and preparation method thereof |
| CN107987322A (en) * | 2017-12-21 | 2018-05-04 | 苏州星火丰盈环保包装有限公司 | A kind of preparation method of biodegradable mulch |
| CN110437501A (en) * | 2019-07-04 | 2019-11-12 | 中国石化长城能源化工（宁夏）有限公司 | A kind of preparation method and application for PVA film environment-friendly plasticizer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103203934B (en) | Heat shrinkage copolyester film and preparation method thereof | |
| CN101367285B (en) | Polyester film and methods for making same | |
| CN102532595A (en) | Compounded plasticizer for thermoplastic processing and method for plasticizing polyvinyl alcohol | |
| CN103483785B (en) | A kind of PETG heat-shrinkable film and preparation method thereof | |
| KR102263881B1 (en) | Co-extruded multi-layer polyester films having hydrolytic stability and improved delamination resistance | |
| CN104608443A (en) | Processing technology for heat shrinkable film | |
| CN111716857A (en) | Melt co-extrusion multilayer composite high-barrier film, preparation method and application thereof | |
| CN104371296A (en) | Poly-methyl ethylene carbonate composition and preparation method thereof | |
| CN106317568A (en) | Anti-ultraviolet PE heat shrinkable film and preparing method thereof | |
| CN102285176A (en) | High-transparency flame-resistant BOPP (Biaxially Oriented Poly Propylene) film and manufacturing process thereof | |
| CN106398132A (en) | Anti-ultraviolet PET heat shrinkable film and preparation method thereof | |
| CN113045881A (en) | Thermal-shrinkage degradable environment-friendly film material and preparation method and application method thereof | |
| CN103009761A (en) | Polyolefin heat-shrinkable film with high shrinking percentage and manufacturing method thereof | |
| CN102718951B (en) | Preparation technologies of double-acid-single-alcohol copolymerization modification PET-A and unidirectional heat shrinkable film thereof | |
| CN201587630U (en) | Extinction blocking five-layer coextruded composite film | |
| CN103753825A (en) | Production method of multilayer co-extruded low-temperature shrinkable polyolefin heat-shrinkable film | |
| CN101607459B (en) | BOPET film capable of being directly heat-sealed | |
| CN111825937A (en) | Thermoplastic polyvinyl alcohol material and processing method thereof | |
| CN106827568A (en) | A kind of polyester film production technology of use reclaimed materials | |
| CN112356543A (en) | High-gloss and high-transparency polyethylene cast film and preparation method thereof | |
| CN110920188A (en) | Bio-based PTT/PLA heat-shrinkable label film and preparation method thereof | |
| CN106398133A (en) | Antistatic PET heat shrinkable film and preparation method thereof | |
| CN106009185A (en) | PE (Poly Ethylene) heat shrink film and preparation method thereof | |
| CN112848580B (en) | PETG/PET co-extrusion self-sealing multilayer film and preparation method thereof | |
| CN112959782B (en) | Completely degradable gas barrier air cushion film with excellent processing performance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201027 |
|
| RJ01 | Rejection of invention patent application after publication |