CN109881285A - A kind of biodegrade PVA melt spinning resin and preparation method thereof - Google Patents
A kind of biodegrade PVA melt spinning resin and preparation method thereof Download PDFInfo
- Publication number
- CN109881285A CN109881285A CN201910070485.4A CN201910070485A CN109881285A CN 109881285 A CN109881285 A CN 109881285A CN 201910070485 A CN201910070485 A CN 201910070485A CN 109881285 A CN109881285 A CN 109881285A
- Authority
- CN
- China
- Prior art keywords
- parts
- pva
- melt spinning
- biodegrade
- acid
- 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
- 238000002074 melt spinning Methods 0.000 title claims abstract description 34
- 239000011347 resin Substances 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 68
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000004014 plasticizer Substances 0.000 claims abstract description 22
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 18
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 18
- 239000003112 inhibitor Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- 239000002667 nucleating agent Substances 0.000 claims abstract description 11
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 229960003511 macrogol Drugs 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 238000006136 alcoholysis reaction Methods 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 5
- 235000010755 mineral Nutrition 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 238000005491 wire drawing Methods 0.000 claims description 5
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims description 3
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 3
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000011670 zinc gluconate Substances 0.000 claims description 3
- 235000011478 zinc gluconate Nutrition 0.000 claims description 3
- 229960000306 zinc gluconate Drugs 0.000 claims description 3
- 239000011576 zinc lactate Substances 0.000 claims description 3
- 229940050168 zinc lactate Drugs 0.000 claims description 3
- 235000000193 zinc lactate Nutrition 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 3
- 244000248349 Citrus limon Species 0.000 claims 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 239000011701 zinc Substances 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 235000016804 zinc Nutrition 0.000 claims 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 54
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 2
- 239000011746 zinc citrate Substances 0.000 description 2
- 235000006076 zinc citrate Nutrition 0.000 description 2
- 229940068475 zinc citrate Drugs 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
Abstract
The present invention relates to a kind of biodegrade PVA melt spinning resin and preparation method thereof, the parts by weight composition that processes raw material of the melt spinning resin is as follows: 50-75 parts of PVA；Pre- modifying agent 4-6 parts, the pre- modifying agent includes that an at least water-soluble zinc salt A, the mineral nucleating agent B for being dissolved in water at least partially, at least one organic acid C and at least one water-soluble inorganic acid D are combined；20-45 parts of plasticiser；0.01-1.5 parts of decomposing inhibitor；0.05-5 parts of fluorine carbon activity agent；1.0-10 parts of processing aid.Using zinc salt A and mineral nucleating agent B as main component in pre- modifier raw material, what is be added simultaneously generates synergistic effect for modified mixed acid, complexation reaction occurs, form the three-dimensional porous reticular structure of dynamics model, the bonding of more bridgings, increase specific surface area (convenient for melted by heating), also destroy, reduce the presence of the regular strand of polyvinyl alcohol, improve undefined structure ratio, it has been greatly reduced the melting temperature of polyvinyl alcohol simultaneously, has solved the technical problem of thermoplastic processing.
Description
Technical field
The present invention relates to a kind of biodegrade PVA melt spinning resins and preparation method thereof, belong to the processing of PVA modified resin
Technical field.
Background technique
The fusing point and decomposition temperature that the chemical structure of the polyhydroxy strong hydrogen bonding of PVA leads to it are very close to therefore process window
Mouth very little, so PVA resin will not generally be carried out using melt spinning method, and other spinning machine-shaping processes are not only multiple
Miscellaneous, environmental pollution is serious, higher cost, this be can not direct melt-spun the reason of.
The characteristics of PVA be exactly it is pure in great amount of hydroxy group on strand chain, therefore molecule and it is intermolecular form it is a large amount of
Hydrogen bond, crystallinity is high, and fusing point is relatively high, and PVA does not have specific fusing point, will colour when being heated to 200 DEG C to it, 230-
240 DEG C just will appear decomposition, however 160 DEG C of initial temperature just have decomposing phenomenon, so can not melt-out spinning.
Due to, containing a large amount of physical crosslinking points, to realize that the melt spinning of PVA will weaken PVA strand on PVA
Hydrogen bond, reducing PVA fusing point and makes the submissive increase of PVA strand.
Chinese Patent Application No. 201210079070 discloses 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, can produce because of water steaming low boiling point unstable.
Current other papers and patent substantially or with a large amount of water make plasticizer.Present invention seek to address that this technical problem.
Summary of the invention
It is an object of the present invention to solving the deficiencies in the prior art, a kind of biodegrade PVA melt spinning tree is provided
Rouge, the present invention widen the distance of PVA fusing point and decomposition point by pre- modification, improve initial pyrolyzation temperature, improve melt index,
Inhibit small molecule plasticizers migration, introducing inorganic ions can penetrate into that PVA is intermolecular and intramolecular hydrogen bond, can interfere PVA
Intermolecular and intramolecular hydrogen bond improves its melt-processable.
The second object of the present invention is to provide a kind of preparation method of biodegrade PVA melt spinning resin.
The technical solution adopted by the present invention to solve the technical problems is:
The parts by weight composition that processes raw material of a kind of biodegrade PVA melt spinning resin, the melt spinning resin is as follows:
50-75 parts of PVA；
Pre- modifying agent 4-6 parts, the pre- modifying agent includes an at least water-soluble zinc salt A, the mine for being dissolved in water at least partially
Physical property nucleating agent B, at least one organic acid C and at least one water-soluble inorganic acid D are combined；
20-45 parts of plasticiser；
0.01-1.5 parts of decomposing inhibitor；
0.05-5 parts of fluorine carbon activity agent；
1.0-10 parts of processing aid.
Using zinc salt A and mineral nucleating agent B as main component in pre- modifier raw material, while what is be added mixes for modified
It closes acid and generates synergistic effect, complexation reaction occurs, form the three-dimensional porous reticular structure of dynamics model, the bonding of more bridgings,
Specific surface area (convenient for melted by heating) is increased, also destroys, reduce the presence of the regular strand of polyvinyl alcohol, improve without fixed
Type structure proportion, while it being greatly reduced the melting temperature of polyvinyl alcohol, solve the technical problem of thermoplastic processing.
Preferably, the parts by weight composition that processes raw material of the melt spinning resin is as follows:
65 parts of PVA；
5 parts of pre- modifying agent；
30 parts of plasticiser；
0.08 part of decomposing inhibitor；
2.5 parts of fluorine carbon activity agent；
5.0 parts of processing aid.
Preferably, the PVA alcoholysis degree be 85-100%, degree of polymerization 500-3000, average molecular weight 6.5 ten thousand to 8.5 ten thousand,
Volatile matter≤5%, sodium acetate≤2.8%, ash content≤1.0%, aforementioned % are mass percent, pH value 6.5-7.0, partial size 60-
120 mesh.
Preferably, any one of water-soluble zinc salt in zinc citrate, zinc gluconate and zinc lactate；Mineral study
Core agent is na-montmorillonite powder or ca-montmorillonite powder, and the organic acid is appointing in succinic acid, glutaric acid and butane tetracarboxylic acid
It anticipates a kind of or any a variety of, the inorganic acid is dilute sulfuric acid or phosphoric acid, the mass ratio 6: 3: 1: 1 of component A, B, C and D.
Preferably, the plasticizer be glycerine, ethylene glycol, polyethylene glycol 100, polyethylene glycol 200, Liquid Macrogol,
At least two compounding in Macrogol 600, ethyl acetate and 1-4 butanediol.
Preferably, the processing aid is zinc stearate, calcium stearate, magnesium stearate, oleamide and methacrylic acid
At least one of methyl esters.
Preferably, the decomposing inhibitor be 3 methyl miaow Cuo tetraborate of 1- butyl, 3 methyl miaow Cuo villaumite of 1- butyl and
At least one of 1- vinyl -3- ethyl miaow Cuo borate.
Preferably, the fluorine carbon activity agent is in Du Pont FSO-100, FSO-100, FS-31 and Noah's ark chemistry AC-702
Any one.
A kind of preparation method of biodegrade PVA melt spinning resin, the method comprises the following steps:
The pre- modification of step S1, PVA:
The PVA of formula ratio is uniformly mixed with the pre- modifying agent of formula ratio, is heated while stirring 10- in 40-60 DEG C of constant temperature
20min；
Step S2, pre- plasticising processing:
The plasticizer of formula ratio, heating side stirring plasticising pretreatment 10- at 40-120 DEG C are added in the material of step S1
40min；
Step S3, fusion plastification squeeze out:
The decomposing inhibitor of formula ratio, the agent of fluorine carbon activity and processing aid are added in the material of step S2, temperature control
At 40-220 DEG C, wire-drawing shape is squeezed out.
The beneficial effects of the present invention are: the present invention widens the distance of PVA fusing point and decomposition point by pre- modification, improve initial
Thermal decomposition temperature improves melt index, inhibits small molecule plasticizers migration, it is intermolecular that introducing inorganic ions can penetrate into PVA
And intramolecular hydrogen bond, PVA can be interfered intermolecular and intramolecular hydrogen bond, improve its melt-processable.At the beginning of the present invention realizes PVA
Beginning decomposition temperature >=200 DEG C, 40 DEG C -220 DEG C of processing temperature.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.
Embodiment 1:
The parts by weight composition that processes raw material of a kind of biodegrade PVA melt spinning resin, the melt spinning resin is as follows:
50 parts of PVA；
4 parts of pre- modifying agent, the pre- modifying agent include water-soluble zinc salt A, mineral nucleating agent B, organic acid C and water solubility
Inorganic acid D is combined；
20 parts of plasticiser；
0.01 part of decomposing inhibitor；
0.05 part of fluorine carbon activity agent；
1.0 parts of processing aid
In the present invention, the PVA alcoholysis degree is that 85 and 100% account for 40% and 60% respectively, and degree of polymerization 500-550 puts down
Average molecular weight 6.5 ten thousand to 6.8 ten thousand, volatile matter≤5%, sodium acetate≤2.8%, ash content≤1.0%, aforementioned % are quality percentage
Than, pH value 6.5, partial size 60-70 mesh；
Water-soluble zinc salt is selected from zinc citrate；Mineralogy nucleating agent is na-montmorillonite powder, and the organic acid is succinic acid,
The inorganic acid is dilute sulfuric acid, the mass ratio 6: 3: 1: 1 of component A, B, C and D.
The plasticizer is the compounding of glycerine, ethylene glycol.
The processing aid is zinc stearate, and the decomposing inhibitor is 3 methyl miaow Cuo tetraborate of 1- butyl, the fluorine
Carbon activity agent is selected from Du Pont FSO-100.
The preparation method of 1 biodegrade PVA melt spinning resin of embodiment, the method comprises the following steps:
The pre- modification of step S1, PVA:
The PVA of formula ratio is uniformly mixed with the pre- modifying agent of formula ratio, is heated while stirring 20min in 40 DEG C of constant temperature；
Step S2, pre- plasticising processing:
The plasticizer of formula ratio, heating side stirring plasticising pretreatment 40min at 40 DEG C are added in the material of step S1；
Step S3, fusion plastification squeeze out:
The decomposing inhibitor of formula ratio, the agent of fluorine carbon activity and processing aid are added in the material of step S2, temperature control
At 40 DEG C, wire-drawing shape is squeezed out.
Embodiment 2
The parts by weight composition that processes raw material of a kind of biodegrade PVA melt spinning resin, the melt spinning resin is as follows:
75 parts of PVA；
6 parts of pre- modifying agent, the pre- modifying agent include water-soluble zinc salt A, mineral nucleating agent B, organic acid C and water solubility
Inorganic acid D is combined；
45 parts of plasticiser；
1.5 parts of decomposing inhibitor；
5 parts of fluorine carbon activity agent；
10 parts of processing aid.
The PVA alcoholysis degree is that 85 and 100% respectively account for 50%, degree of polymerization 2900-3000, average molecular weight 8.0 ten thousand to
8.5 ten thousand, volatile matter≤5%, sodium acetate≤2.8%, ash content≤1.0%, aforementioned % is mass percent, pH value 7.0, partial size
110-120 mesh, water-soluble zinc salt are selected from zinc gluconate；Mineralogy nucleating agent is ca-montmorillonite powder, and the organic acid is penta
Diacid, the inorganic acid are phosphoric acid, the mass ratio 6: 3: 1: 1 of component A, B, C and D.
The plasticizer is the compounding of polyethylene glycol 100, polyethylene glycol 200.
The processing aid is magnesium stearate.
The decomposing inhibitor is 3 methyl miaow Cuo villaumite of 1- butyl.
The fluorine carbon activity agent is selected from FSO-100.
The preparation method of 2 biodegrade PVA melt spinning resin of embodiment, the method comprises the following steps:
The pre- modification of step S1, PVA:
The PVA of formula ratio is uniformly mixed with the pre- modifying agent of formula ratio, is heated while stirring 10min in 60 DEG C of constant temperature；
Step S2, pre- plasticising processing:
The plasticizer of formula ratio, heating side stirring plasticising pretreatment 10min at 120 DEG C are added in the material of step S1；
Step S3, fusion plastification squeeze out:
The decomposing inhibitor of formula ratio, the agent of fluorine carbon activity and processing aid are added in the material of step S2, temperature control
At 220 DEG C, wire-drawing shape is squeezed out.
Embodiment 3
The parts by weight composition that processes raw material of a kind of biodegrade PVA melt spinning resin, the melt spinning resin is as follows:
65 parts of PVA；
5 parts of pre- modifying agent；
30 parts of plasticiser；
0.08 part of decomposing inhibitor；
2.5 parts of fluorine carbon activity agent；
5.0 parts of processing aid.
The PVA alcoholysis degree is that 85 and 100% account for 70% and 30%, degree of polymerization 1800-2000, average molecular weight respectively
7.5 ten thousand to 7.8 ten thousand, volatile matter≤5%, sodium acetate≤2.8%, ash content≤1.0%, aforementioned % is mass percent, pH value
6.8,80 mesh of partial size.
Water-soluble zinc salt is selected from zinc lactate；Mineralogy nucleating agent is ca-montmorillonite powder, and the organic acid is butane tetracarboxylic
Acid, the inorganic acid are dilute sulfuric acid, the mass ratio 6: 3: 1: 1 of component A, B, C and D.
The plasticizer is the compounding of Liquid Macrogol, Macrogol 600.
The processing aid is the compounding of oleamide and methyl methacrylate.
The decomposing inhibitor is 1- vinyl -3- ethyl miaow Cuo borate.
The fluorine carbon activity agent is selected from Noah's ark chemistry AC-702.
The preparation method of the biodegradable PVA melt spinning resin of embodiment 3, the method comprises the following steps:
The pre- modification of step S1, PVA:
The PVA of formula ratio is uniformly mixed with the pre- modifying agent of formula ratio, is heated while stirring 15min in 50 DEG C of constant temperature；
Step S2, pre- plasticising processing:
The plasticizer of formula ratio, heating side stirring plasticising pretreatment 20min at 80 DEG C are added in the material of step S1；
Step S3, fusion plastification squeeze out:
The decomposing inhibitor of formula ratio, the agent of fluorine carbon activity and processing aid are added in the material of step S2, temperature control
At 150 DEG C, wire-drawing shape is squeezed out.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (9)
1. a kind of biodegrade PVA melt spinning resin, it is characterised in that: the parts by weight that process raw material of the melt spinning resin
It forms as follows:
50-75 parts of PVA；
Pre- modifying agent 4-6 parts, the pre- modifying agent includes an at least water-soluble zinc salt A, the mineral for being dissolved in water at least partially
Nucleating agent B, at least one organic acid C and at least one water-soluble inorganic acid D are combined；
20-45 parts of plasticiser；
0.01-1.5 parts of decomposing inhibitor；
0.05-5 parts of fluorine carbon activity agent；
1.0-10 parts of processing aid.
2. biodegrade PVA melt spinning resin according to claim 1, it is characterised in that: the melt spinning resin
Process raw material parts by weight composition it is as follows:
65 parts of PVA；
5 parts of pre- modifying agent；
30 parts of plasticiser；
0.08 part of decomposing inhibitor；
2.5 parts of fluorine carbon activity agent；
5.0 parts of processing aid.
3. biodegrade PVA melt spinning resin according to claim 1 or 2, it is characterised in that: the PVA alcoholysis degree
For 85-100%, degree of polymerization 500-3000, average molecular weight 6.5 ten thousand to 8.5 ten thousand, volatile matter≤5%, sodium acetate≤2.8%, ash
Dividing≤1.0%, aforementioned % is mass percent, pH value 6.5-7.0, partial size 60-120 mesh.
4. biodegrade PVA melt spinning resin according to claim 1, it is characterised in that: water-soluble zinc salt is selected from lemon
Any one in lemon acid zinc, zinc gluconate and zinc lactate；Mineralogy nucleating agent is na-montmorillonite powder or ca-montmorillonite
Powder, the organic acid be in succinic acid, glutaric acid and butane tetracarboxylic acid any one or it is any a variety of, the inorganic acid is dilute
Sulfuric acid or phosphoric acid, the mass ratio 6: 3: 1: 1 of component A, B, C and D.
5. biodegrade PVA melt spinning resin according to claim 1, it is characterised in that:: the plasticizer is the third three
Alcohol, ethylene glycol, polyethylene glycol 100, polyethylene glycol 200, Liquid Macrogol, Macrogol 600, ethyl acetate and 1-4 butanediol
In at least two compounding.
6. biodegrade PVA melt spinning resin according to claim 1, it is characterised in that: the processing aid is hard
At least one of resin acid zinc, calcium stearate, magnesium stearate, oleamide and methyl methacrylate.
7. biodegrade PVA melt spinning resin according to claim 1, it is characterised in that: the decomposing inhibitor is
In 3 methyl miaow Cuo tetraborate of 1- butyl, 3 methyl miaow Cuo villaumite of 1- butyl and 1- vinyl -3- ethyl miaow Cuo borate extremely
Few one kind.
8. biodegrade PVA melt spinning resin according to claim 1, it is characterised in that: the fluorine carbon activity agent choosing
From any one in Du Pont FSO-100, FSO-100, FS-31 and Noah's ark chemistry AC-702.
9. a kind of preparation method of biodegrade PVA melt spinning resin described in any one of claim 1-9, feature exist
In: the method comprises the following steps:
The pre- modification of step S1, PVA:
The PVA of formula ratio is uniformly mixed with the pre- modifying agent of formula ratio, is heated while stirring 10- in 40-60 DEG C of constant temperature
20min；
Step S2, pre- plasticising processing:
The plasticizer of formula ratio, heating side stirring plasticising pretreatment 10- at 40-120 DEG C are added in the material of step S1
40min；
Step S3, fusion plastification squeeze out:
The decomposing inhibitor of formula ratio, the agent of fluorine carbon activity and processing aid are added in the material of step S2, temperature control exists
40-220 DEG C, squeeze out wire-drawing shape.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910070485.4A CN109881285A (en) | 2019-01-24 | 2019-01-24 | A kind of biodegrade PVA melt spinning resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910070485.4A CN109881285A (en) | 2019-01-24 | 2019-01-24 | A kind of biodegrade PVA melt spinning resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109881285A true CN109881285A (en) | 2019-06-14 |
Family
ID=66926798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910070485.4A Pending CN109881285A (en) | 2019-01-24 | 2019-01-24 | A kind of biodegrade PVA melt spinning resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109881285A (en) |
Cited By (2)
| 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 |
| CN113501979A (en) * | 2021-07-15 | 2021-10-15 | 江南大学 | High-temperature water-soluble fiber-opening sea-island fiber fabric and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409837A (en) * | 2013-08-02 | 2013-11-27 | 东华大学 | Method for preparing water soluble polyvinyl alcohol fiber through melt spinning |
| CN103819884A (en) * | 2012-11-16 | 2014-05-28 | 上海载和实业投资有限公司 | Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof |
| CN104073903A (en) * | 2014-07-08 | 2014-10-01 | 世源科技(嘉兴)医疗电子有限公司 | High-temperature water soluble melt spinning flame retardant polyvinyl alcohol fiber and application thereof |
| CN108424601A (en) * | 2018-04-24 | 2018-08-21 | 山东科贝尔非织造材料科技有限公司 | The water-solubility PVA of composite fibre melt-processable is sliced and its preparation process |
| CN109181186A (en) * | 2018-11-12 | 2019-01-11 | 洪春 | A kind of biodegradable hydrophobicity PVA resin composite materials |
-
2019
- 2019-01-24 CN CN201910070485.4A patent/CN109881285A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819884A (en) * | 2012-11-16 | 2014-05-28 | 上海载和实业投资有限公司 | Novel heat-resistant high-toughness polylactic acid composite material and preparation method thereof |
| CN103409837A (en) * | 2013-08-02 | 2013-11-27 | 东华大学 | Method for preparing water soluble polyvinyl alcohol fiber through melt spinning |
| CN104073903A (en) * | 2014-07-08 | 2014-10-01 | 世源科技(嘉兴)医疗电子有限公司 | High-temperature water soluble melt spinning flame retardant polyvinyl alcohol fiber and application thereof |
| CN108424601A (en) * | 2018-04-24 | 2018-08-21 | 山东科贝尔非织造材料科技有限公司 | The water-solubility PVA of composite fibre melt-processable is sliced and its preparation process |
| CN109181186A (en) * | 2018-11-12 | 2019-01-11 | 洪春 | A kind of biodegradable hydrophobicity PVA resin composite materials |
Cited By (3)
| 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 |
| CN113501979A (en) * | 2021-07-15 | 2021-10-15 | 江南大学 | High-temperature water-soluble fiber-opening sea-island fiber fabric and preparation method thereof |
| CN113501979B (en) * | 2021-07-15 | 2022-05-20 | 江南大学 | High-temperature water-soluble splitting sea-island fiber fabric and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109456555B (en) | Blow molding water-soluble polyvinyl alcohol film and preparation method and application thereof | |
| CN105385124B (en) | Carbon fiber reinforced polylactic acid 3D printing material and preparation method thereof | |
| EP3068832B1 (en) | Polyamide moulding compounds for large moulded parts | |
| CN102234405B (en) | Water-resistant polyvinyl alcohol (PVA) film composition as well as fusion preparation method thereof | |
| CN104448641B (en) | Polyvinyl alcohol wire for fused deposition molding and processing method of polyvinyl alcohol wire | |
| CN105602011A (en) | High-compatibility starch-based full-biodegradable resin, and preparation method thereof | |
| CN109881285A (en) | A kind of biodegrade PVA melt spinning resin and preparation method thereof | |
| CN103991217A (en) | 3D printing molding method | |
| KR20150134355A (en) | Water-soluble polymer and polymer internal lubricant | |
| CN110172221A (en) | A kind of starch base melt spinning resin and its application | |
| CN107201012A (en) | A kind of low temperature PLA bases 3D printing wire rod and preparation method thereof | |
| CN109608815A (en) | A kind of 3D printing low smell ABS material and preparation method thereof | |
| CN105504704A (en) | Ethanolamine activated Na-montmorillonite and polymer composite biodegradable film blowing resin and preparation method | |
| CN107353550A (en) | A kind of 3D printing backing material and preparation method thereof | |
| CN114989581B (en) | Biodegradable polylactic acid foaming particle and preparation method thereof | |
| CN109825016A (en) | A kind of biodegrade PVA stretch wrap film and preparation method thereof | |
| CN103469678A (en) | Preparation method of recyclable coated paper | |
| CN105440521A (en) | Thermoplastic modified polyvinyl alcohol resin and preparation method thereof | |
| CN105440524B (en) | A kind of thermoplastic modification polyvinyl alcohol resin and preparation method thereof | |
| CN103965600B (en) | A kind of method of the toughness reinforcing heat resistance modified polylactic acid of plant base composite environment-friendly modifying agent | |
| DE3923704C2 (en) | ||
| CN105273239A (en) | Cellulose diacetate composite material and preparation method thereof | |
| CN106589862A (en) | Wood-imitation material for 3D printing and preparation method thereof | |
| CN102604290B (en) | Polyvinyl alcohol material of melt-processable and preparation method thereof | |
| CN107641107B (en) | Diacetyl epoxy glyceryl undecanoate and preparation method and application 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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210120 Address after: 255000 room 1103, unit 1, building 3, 77 Liuquan Road, Zhangdian District, Zibo City, Shandong Province Applicant after: Zhu Pengtao Address before: 236500 No. 797, Renmin East Road, Jieshou City, Fuyang City, Anhui Province Applicant before: ANHUI DINGYANG BIO-BASED MATERIALS Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190614 |
|
| RJ01 | Rejection of invention patent application after publication |