CN110079891A - A kind of biodegradable PVA melt spinning resin and its application - Google Patents

A kind of biodegradable PVA melt spinning resin and its application Download PDF

Info

Publication number
CN110079891A
CN110079891A CN201910368605.9A CN201910368605A CN110079891A CN 110079891 A CN110079891 A CN 110079891A CN 201910368605 A CN201910368605 A CN 201910368605A CN 110079891 A CN110079891 A CN 110079891A
Authority
CN
China
Prior art keywords
pva
parts
melt spinning
biodegradable
spinning resin
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
Application number
CN201910368605.9A
Other languages
Chinese (zh)
Inventor
李芳丽
朱春英
张兆洋
孙文奇
张万虎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Huilan Environmental Protection Technology Co Ltd
Original Assignee
Suzhou Huilan Environmental Protection Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Suzhou Huilan Environmental Protection Technology Co Ltd filed Critical Suzhou Huilan Environmental Protection Technology Co Ltd
Priority to CN201910368605.9A priority Critical patent/CN110079891A/en
Publication of CN110079891A publication Critical patent/CN110079891A/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/007—Addition polymers

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A kind of biodegradable PVA melt spinning resin and its application, each ingredient and parts by weight of the PVA melt spinning resin are as follows: 55-80 parts of PVA, 20-45 parts of plasticiser, 1.0-2.5 parts of decomposing inhibitor, 0.5-5 parts of fluorine carbon activity agent, 1.0-10 parts of processing aid.By being modified to PVA in the present invention, its fusing point and decomposition point distance are widened, initial pyrolyzation temperature is improved, improve melt index, inhibit small molecule plasticizers migration, the PVA melt spinning resin of acquisition has completely biodegradable, also has high-temperature water-soluble, it can be directly used for melt spinning, simple process, equipment investment is few, does not use organic solvent or coagulating bath, save the energy, and no three wastes pollution on the environment.

Description

A kind of biodegradable PVA melt spinning resin and its application
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of biodegradable PVA melt spinning resin and its Using.
Background technique
PVA (polyvinyl alcohol) due to good biological degradability, it is current solve because of plastic product it is discarded after caused by White pollution in terms of have broad application prospects.But compared with other macromolecule resin materials, since PVA resin can not be into Row melt spinning, so significantly limiting its application range.
Since PVA (polyvinyl alcohol) has the chemical structure of polyhydroxy strong hydrogen bonding, lead to its fusing point and decomposition temperature very It is close, therefore, process window very little, so PVA spinning cannot generally be carried out using melt spinning method.PVA so far is spun Silk mostly uses wet spinning, gel spinning or dry spinning, these spinning process belong to solwution method, and complex process is thrown Money is big, and environmental pollution is serious；
There is great amount of hydroxy group on the strand of PVA, molecule and it is intermolecular form a large amount of hydrogen bond, crystallinity is high, Since PVA does not have specific fusing point, therefore for 200-220 DEG C, PVA can not usually carry out melt-out spinning to initial pyrolyzation temperature. Due to being physical crosslinking points containing a large amount of on PVA strand, to realization PVA melt spinning it is necessary to weaken PVA strand hydrogen bond, PVA fusing point is reduced, strand flexibility is increased.
Chinese patent CN102776597 is related to a kind of high strength high modulus polyvinyl alcohol fiber and its melt spinning method, can be with Melting extrusion, but PVA powder does plasticizer addition polyalcohol with water, substantially still falls within solwution method spinning, is only made with water For solvent, and produce because of the low boiling point of water and unstable.
It is modified currently, referring in the prior art using polyalcohol and oligomer, but with a large amount of water as solvent, and simultaneously Do not illustrate the origin of polyalcohol and oligomer, can not judge the practicality.
Summary of the invention
The purpose of the present invention is to provide a kind of biodegradable PVA melt spinning resins and its application, by PVA Resin is modified, and widens the fusing point and decomposition point distance of PVA, is improved melt index, is made its initial pyrolyzation temperature >=245 DEG C, melt index reaches 10-50g/10min (test condition: 210 DEG C, 5.0Kg), and the PVA melt spinning resin of acquisition has had Complete biodegradable also has high-temperature water-soluble, can carry out melt spinning, and simple process, equipment investment is few, without using solvent or The energy, and no three wastes pollution on the environment are saved in person's coagulating bath.
In order to achieve the above object, the invention provides the following technical scheme:
A kind of biodegradable PVA melt spinning resin, each ingredient and its parts by weight contained are as follows: PVA 55-80 Part, 20-45 parts of plasticiser, 1.0-2.5 parts of decomposing inhibitor, 0.5-5 parts of fluorine carbon activity agent, 1.0-10 parts of processing aid；Wherein, The plasticiser is compound system comprising by propylene oxide, polyglycereol or PEG 100-20000, pentaerythrite, 1-4 fourth two Alcohol, diethylene glycol (DEG), in trimethylolpropane three kinds or more and deionized water addition reaction product, the addition reaction product with it is sweet Oil, polyglycereol or PEG100-20000 are compounded；Wherein, addition reaction temperature is 60~85 DEG C, and the reaction time is that 1.5-6 is small When, addition reaction product is no less than 10 parts when compounding.
Further, the alcoholysis degree of the PVA is 85%-100%, degree of polymerization 500-3000, average molecular weight 65000- 85000, volatile matter≤5%, sodium acetate≤2.8, ash content≤1.0, pH value 6.5-7.0, partial size 80-500 mesh.
Also, the PVA that the PVA is 500-800 by the degree of polymerization is compounded with the PVA that the degree of polymerization is 1200-3000, the two Weight ratio be the degree of polymerization be 500-800 PVA: the degree of polymerization be 1200-3000 PVA=1:2-2.5.
Preferably, the decomposing inhibitor is selected from 1- butyl -3- methyl miaow Cuo tetrafluoroborate, 1- vinyl -3- ethyl Miaow Cuo borate, 1- ethoxy -3- methyl miaow Cuo tetrafluoroborate, 1- butyl -3- methyl miaow Cuo villaumite, 1- vinyl 3- ethyl Miaow Cuo smelling salts, dodecyl sulfobetaine, graphene, graphene oxide and rutile/anatase TiO2In at least one Kind.
Further, 1- butyl -3- methyl miaow Cuo tetrafluoroborate in the decomposing inhibitor: 1- butyl -3- methyl miaow Cuo Villaumite=1-2:1, weight ratio, the compounding of the two can effectively improve temperature of initial decomposition, while can also effectively drop The water imbibition of low PVA.
Also, the fluorine carbon activity agent in Du Pont FSO-100, Du Pont FS-31 and Noah's ark chemistry AC-702 at least one Kind.
Further, the processing aid be lubricant, antioxidant, flow improver additive and heat stabilizer at least two kinds with On.
Also, the heat stabilizer is zinc stearate, calcium stearate, magnesium stearate or methyl methacrylate；The antioxygen Agent is antioxidant 1010, irgasfos 168, antioxidant 300, antioxidant 330, a variety of mixtures in TNP；The lubricant or stream Dynamic promotor is selected from least one of oleamide, erucyl amide, stearic amide.
Biodegradable PVA melt spinning resin of the present invention is used to prepare non-woven fabrics.
The present invention passes through the mutual synergistic effect of plasticiser and decomposing inhibitor described above, can effectively widen fusing point With decomposition point distance, initial pyrolyzation temperature is improved, improves melt index, the small molecule solvent (decomposing inhibitor) of introducing, energy It is intermolecular enough to penetrate into PVA, destroys its Van der Waals force, improves spin-drawing rate.
In plasticiser of the invention, low molecular weight glycerol and high molecular weight polyglycereol (polyglycereol 10/9/8/7/6/5/ is added 4//3) appearance effects caused by small molecule plasticizers migration or PEG (PEG100-20000 etc.), are reduced.
Compared with prior art, the invention has the following beneficial effects:
In biodegradable PVA melt spinning resin of the invention, by being modified to PVA, successfully realize PVA's Fusion plastification squeezes out, and melt index reaches 10-45g/10min (test condition: 210 DEG C, 5.0Kg), and temperature of initial decomposition >= 245 DEG C, 140 DEG C -250 DEG C of processing temperature；With completely biodegradable, degradability will not be influenced because of modified generation crosslinking due to.
PVA melt spinning resin of the invention can be directly used for melt spinning, not use solvent or coagulating bath, save energy Source, and three-waste free discharge, simple process, equipment investment is few, and occupied area is small, low production cost.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
By 15 parts of pentaerythrite, 15 parts of 1,4-butanediol, 10 parts of diethylene glycol (DEG), 25 parts of deionized water, it is added separately to react It being stirred evenly in kettle, is added dropwise 35 parts of propylene oxide, and 0.015 part of phosphoric acid catalyst is added and carries out addition reaction, revolving speed is 80~ 100 revs/min, mixing time is 100~120 minutes, and temperature is 60~85 DEG C, obtains addition reaction product one.
By 20 parts of PVA0599,40 parts of PVA1299, one 10 parts of the addition reaction product of embodiment 1, gathers by 15 parts of glycerine 6 10 parts of glycerol, 5 parts of deionized water, 1.5 parts of tetrafluoroborate of methyl miaow Cuo of 1- butyl -3-, dodecyl sulfobetaine 1.0 Part, anatase titanium dioxide TiO22.0 parts, 0.45 part of zinc stearate, 1.0 parts of oleamide, 1.5 parts of Du Pont FSO-100, antioxidant 1010 0.4 part, 0.5 part of antioxidant 300, SiO20.2 part, put into high-speed mixer, heat while stirring respectively, 40 DEG C- Plasticising is given under 120 DEG C/40min state, is placed 24 hours, then put into pelletizer and be granulated, is obtained biodegradable PVA melt spinning Resin.
Examination spinning, 140 DEG C of melt processing temperature-are carried out on single unit spinning machine with biodegrade PVA melt spinning resin 250 DEG C, spinneret extruded velocity 0.5-1.0m/min, 5-8 times of drafting multiple, performance parameter is as shown in table 1.
Embodiment 2
By 25 parts of an acetoglyceride, two 25 parts of acetoglycerides, 25 parts of triacetyl glycerine, 25 parts of glycerine adds respectively Enter in reaction kettle and stir evenly, 0.01 part of phosphoric acid catalyst is added and carries out addition reaction, revolving speed is 80~100 revs/min, stirring Time is 100~120 minutes, and temperature is 60~85 DEG C, obtains addition reaction product two.
By 20 parts of PVA0899,40 parts of PVA1799,2 15 parts of the addition reaction product of embodiment 2,10 parts of glycerine, 10 parts of PEG800,5 parts of deionized water, 1- butyl -3- methyl miaow Cuo villaumite, 1.5 parts, 1.0 parts of dodecyl sulfobetaine, Anatase titanium dioxide TiO22.0 parts, 0.45 part of zinc stearate, 1.5 parts of amide are resolved, 1.5 parts of antioxidant 1010s 0.6 of Du Pont FS-31 Part, antioxidant 300/0.3 part, SiO2It/0.5 part, puts into high-speed mixer, heats while stirring respectively, at 40 DEG C -120 DEG C/40min state under give plasticising, place 24 hours, then put into pelletizer and be granulated, obtain biodegrade PVA melt spinning tree Rouge.
Examination spinning, 140 DEG C of melt processing temperature-are carried out on single unit spinning machine with biodegrade PVA melt spinning resin 250 DEG C, spinneret extruded velocity 0.5-1.0m/min, 5-8 times of drafting multiple, performance parameter is as shown in table 1.
Embodiment 3
By 20 parts of PVA0599,40 parts of PVA2099,2 25 parts of the addition reaction product of embodiment 2,5 parts of glycerine, 5 parts of PEG2000,5 parts of deionized water, 1.0 parts of tetrafluoroborate of methyl miaow Cuo of 1- butyl -3-, 1- butyl -3- methyl miaow Cuo chlorine 1.0 parts of salt, 1.0 parts of dodecyl sulfobetaine, anatase titanium dioxide TiO22.0 parts, 0.45 part of zinc stearate, oleamide 1.0 Part, Du Pont FSO-1001.5 parts, 0.6 part of antioxidant 1010,0.3 part of antioxidant 300, SiO20.5 part, height is put into respectively It in fast mixing machine, heats while stirring, plasticising is given under 40 DEG C -120 DEG C/40min state, place 24 hours, then put into granulation It is granulated in machine, obtains biodegrade PVA melt spinning resin.
Examination spinning is carried out on single unit spinning machine with biodegrade PVA melt spinning resin, performance parameter is as shown in table 1.
Embodiment 4
By 20 parts of PVA0588,40 parts of PVA2088, one 30 parts of the addition reaction product of embodiment 1,5 parts of glycerine, 5 parts of PEG2000,1.5 parts of tetrafluoroborate of methyl miaow Cuo of 1- butyl -3-, 1.0 parts of villaumite of methyl miaow Cuo of 1- butyl -3-, 12 1.5 parts of alkyl sulfo betaines, anatase titanium dioxide TiO22.0 parts, 0.45 part of zinc stearate, 1.0 parts of oleamide, Du Pont FSO-100 1.5 parts, antioxidant 1010/0.6 part, 0.3 part of antioxidant 300, SiO2It 0.5 part, puts into high-speed mixer respectively, while stirring Side heating is mixed, plasticising is given under 40 DEG C -120 DEG C/40min state, places 24 hours, then put into pelletizer and be granulated, is given birth to Object degradation PVA melt spinning resin.
Examination spinning, 140 DEG C of melt processing temperature-are carried out on single unit spinning machine with biodegrade PVA melt spinning resin 250 DEG C, spinneret extruded velocity 0.5-1.0m/min, 5-8 times of drafting multiple, performance parameter is as shown in table 1.
Table 1

Claims (10)

1. a kind of biodegradable PVA melt spinning resin, each ingredient and its parts by weight contained are as follows: PVA55-80 parts, 20-45 parts of plasticiser, 1.0-2.5 parts of decomposing inhibitor, 0.5-5 parts of fluorine carbon activity agent, 1.0-10 parts of processing aid；
Wherein, the plasticiser be compound system comprising by propylene oxide, polyglycereol or PEG100-20000, pentaerythrite, 1-4 butanediol, diethylene glycol (DEG), in trimethylolpropane three kinds or more and deionized water addition reaction product, which produces Object is compounded with glycerol, polyglycereol or PEG100-20000；Wherein, addition reaction temperature is 60~85 DEG C, and the reaction time is 1.5-6 hours, addition reaction product was no less than 10 parts when compounding.
2. biodegradable PVA melt spinning resin according to claim 1, which is characterized in that the alcoholysis degree of the PVA 85%-100%, degree of polymerization 500-3000, average molecular weight 65000-85000, volatile matter≤5%, sodium acetate≤2.8, ash content ≤ 1.0, pH value 6.5-7.0, partial size 80-500 mesh.
3. biodegradable PVA melt spinning resin according to claim 1 or claim 2, which is characterized in that the PVA is by gathering The right PVA for being 500-800 is compounded with the PVA that the degree of polymerization is 1200-3000, and the weight ratio of the two is that the degree of polymerization is 500- 800 PVA: the degree of polymerization is the PVA=1:2-2.5 of 1200-3000.
4. biodegradable PVA melt spinning resin according to claim 1, which is characterized in that the fluorine carbon activity agent Selected from least one of Du Pont FSO-100, Du Pont FS-31 and Noah's ark chemistry AC-702.
5. biodegradable PVA melt spinning resin according to claim 1, which is characterized in that the decomposing inhibitor Selected from 1- butyl -3- methyl miaow Cuo tetrafluoroborate, 1- vinyl -3- ethyl miaow Cuo borate, 1- ethoxy -3- methyl miaow Cuo Tetrafluoroborate, 1- butyl -3- methyl miaow Cuo villaumite, 1- vinyl 3- ethyl miaow Cuo smelling salts, dodecyl sulfobetaine, stone Black alkene, graphene oxide and rutile-type or anatase titanium dioxide TiO2At least one of.
6. biodegradable PVA melt spinning resin according to claim 1, which is characterized in that the decomposing inhibitor Middle 1- butyl -3- methyl miaow Cuo tetrafluoroborate: 1- butyl -3- methyl miaow Cuo villaumite=1-2:1, weight ratio.
7. biodegradable PVA melt spinning resin according to claim 1, which is characterized in that the processing aid is At least two or more in lubricant, antioxidant, flow improver additive and heat stabilizer.
8. biodegradable PVA melt spinning resin according to claim 7, which is characterized in that the lubricant or stream Dynamic promotor is selected from least one of oleamide, erucyl amide, stearic amide；The heat stabilizer is selected from stearic acid At least one of zinc, calcium stearate, magnesium stearate and methyl methacrylate.
9. biodegradable PVA melt spinning resin according to claim 8, which is characterized in that the antioxidant is anti- Oxygen agent 1010, irgasfos 168, antioxidant 300, antioxidant 330, a variety of mixtures in TNP.
10. as the described in any item biodegradable PVA melt spinning resins of claim 1-9 are preparing answering in non-woven fabrics With.
CN201910368605.9A 2019-05-05 2019-05-05 A kind of biodegradable PVA melt spinning resin and its application Pending CN110079891A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910368605.9A CN110079891A (en) 2019-05-05 2019-05-05 A kind of biodegradable PVA melt spinning resin and its application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910368605.9A CN110079891A (en) 2019-05-05 2019-05-05 A kind of biodegradable PVA melt spinning resin and its application

Publications (1)

Publication Number Publication Date
CN110079891A true CN110079891A (en) 2019-08-02

Family

ID=67418539

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910368605.9A Pending CN110079891A (en) 2019-05-05 2019-05-05 A kind of biodegradable PVA melt spinning resin and its application

Country Status (1)

Country Link
CN (1) CN110079891A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111876899A (en) * 2020-08-01 2020-11-03 杨春云 Ultra-soft non-woven fabric and preparation method thereof
CN112358655A (en) * 2020-11-09 2021-02-12 绍兴兆丽新材料科技有限公司 Environment-friendly medicine packaging material and preparation method thereof
CN112457535A (en) * 2020-11-30 2021-03-09 绍兴兆丽新材料科技有限公司 Environment-friendly spicy cabbage packaging bag and preparation method thereof
WO2021093691A1 (en) * 2019-11-13 2021-05-20 华南理工大学 Water-soluble polyvinyl alcohol non-woven fabric, preparation method therefor, and application thereof
EP4321669A1 (en) * 2022-08-13 2024-02-14 Aquapak IP Limited Polyvinyl alcohol fibres and spunbond fibrous products

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017699A (en) * 2015-08-06 2015-11-04 潍坊华潍新材料科技有限公司 Biology-base degradable stretching film and preparing method thereof
CN106366355A (en) * 2016-08-31 2017-02-01 朱春英 Starch composite material applicable to melt plasticizing extrusion and preparation method thereof
CN106366357A (en) * 2016-08-31 2017-02-01 朱春英 Starch biology base composite material and preparation method thereof
CN106397841A (en) * 2016-08-31 2017-02-15 朱春英 High-barrier biomaterial and preparation method thereof
CN109181186A (en) * 2018-11-12 2019-01-11 洪春 A kind of biodegradable hydrophobicity PVA resin composite materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017699A (en) * 2015-08-06 2015-11-04 潍坊华潍新材料科技有限公司 Biology-base degradable stretching film and preparing method thereof
CN106366355A (en) * 2016-08-31 2017-02-01 朱春英 Starch composite material applicable to melt plasticizing extrusion and preparation method thereof
CN106366357A (en) * 2016-08-31 2017-02-01 朱春英 Starch biology base composite material and preparation method thereof
CN106397841A (en) * 2016-08-31 2017-02-15 朱春英 High-barrier biomaterial and preparation method thereof
CN109181186A (en) * 2018-11-12 2019-01-11 洪春 A kind of biodegradable hydrophobicity PVA resin composite materials

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021093691A1 (en) * 2019-11-13 2021-05-20 华南理工大学 Water-soluble polyvinyl alcohol non-woven fabric, preparation method therefor, and application thereof
CN111876899A (en) * 2020-08-01 2020-11-03 杨春云 Ultra-soft non-woven fabric and preparation method thereof
CN112358655A (en) * 2020-11-09 2021-02-12 绍兴兆丽新材料科技有限公司 Environment-friendly medicine packaging material and preparation method thereof
CN112457535A (en) * 2020-11-30 2021-03-09 绍兴兆丽新材料科技有限公司 Environment-friendly spicy cabbage packaging bag and preparation method thereof
EP4321669A1 (en) * 2022-08-13 2024-02-14 Aquapak IP Limited Polyvinyl alcohol fibres and spunbond fibrous products
WO2024037988A1 (en) * 2022-08-13 2024-02-22 Aquapak Ip Limited Polyvinyl alcohol fibres and spunbond fibrous products

Similar Documents

Publication Publication Date Title
CN110079891A (en) A kind of biodegradable PVA melt spinning resin and its application
CN110172221A (en) A kind of starch base melt spinning resin and its application
CN102108196B (en) Method for preparing polylactic acid degradable material
CN110129917A (en) A kind of antibacterial starch base melt spinning resin and its application
CN103147159B (en) Preparation method of polylactic acid nanofiber
CN106519311B (en) A kind of thermoplastic starch-polyvinyl alcohol anti-fog thin film and preparation method thereof
CN103409837B (en) The method of water-soluble polyvinyl alcohol fibers prepared by a kind of melt spinning
CN103965596B (en) A kind of biodegradable polylactic acid based composites and application
AU2014242705B2 (en) Water-soluble polymer and polymer internal lubricant
CN108193318A (en) A kind of graphene modified polylactic acid fiber and preparation method thereof
CN105295106A (en) Preparation method of cellulose based 3D printing wire
CN103276472B (en) Collagen/polyvinyl alcohol composite microspheres as well as preparation method and application thereof
CN108456407A (en) A kind of degradable package material and preparation method thereof
CN105001569A (en) Polyvinyl alcohol/shell powder biomass composite material and preparation method therefor
CN102372911A (en) Efficient color master batch composition special for biodegradable plastic and preparation method thereof
CN104262915B (en) Prepare the method for the polylactic acid based plasticising wood plastic composite of low mobility
CN102250389B (en) Biodegradable polymer material compatibilized and blended by lignocellulose and preparation method thereof
CN105368017A (en) High-fluidity PLA bioplastic
CN104559228B (en) Preparation method of graphene oxide reinforced leather solid waste collagen powder/polylactic acid composite
CN109354836A (en) A kind of high intensity antibacterial polyethylene terephthalate plastic cup and preparation method thereof
CN108841151A (en) A kind of biodegradable conducing composite material and preparation method thereof
CN104804225A (en) Method for surface hydroxyl modification of starch and cellulose solid powder
CN106433044A (en) Modified bagasse strengthening PBAT/starch complete biodegradation composite material and preparing method and application thereof
CN102560740A (en) Hydrophilic poly-beta-hydroxybutyrate (PHB) fiber and preparation method thereof
CN105949807A (en) Polyvinyl alcohol-based wood-plastic composite and melting processing 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: 20190802

RJ01 Rejection of invention patent application after publication