CN105440523B - A kind of thermoplastic modification polyvinyl alcohol resin and preparation method thereof - Google Patents
A kind of thermoplastic modification polyvinyl alcohol resin and preparation method thereof Download PDFInfo
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- CN105440523B CN105440523B CN201410515857.7A CN201410515857A CN105440523B CN 105440523 B CN105440523 B CN 105440523B CN 201410515857 A CN201410515857 A CN 201410515857A CN 105440523 B CN105440523 B CN 105440523B
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- vinyl
- monomer
- thermoplastic ethylene
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- modified polyvinylalcohol
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 97
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 95
- 229920005989 resin Polymers 0.000 title claims abstract description 75
- 239000011347 resin Substances 0.000 title claims abstract description 75
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 57
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 9
- 230000004048 modification Effects 0.000 title claims description 6
- 238000006011 modification reaction Methods 0.000 title claims description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 89
- 239000005977 Ethylene Substances 0.000 claims abstract description 53
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 53
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004014 plasticizer Substances 0.000 claims abstract description 25
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 23
- -1 saturated aliphatic dicarboxylic acids ester Chemical class 0.000 claims abstract description 18
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N Triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000011187 glycerol Nutrition 0.000 claims abstract description 15
- 239000008234 soft water Substances 0.000 claims abstract description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 239000000454 talc Substances 0.000 claims abstract description 14
- 229910052623 talc Inorganic materials 0.000 claims abstract description 14
- 235000012222 talc Nutrition 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- UAUDZVJPLUQNMU-KTKRTIGZSA-N (Z)-docos-13-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 19
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 7
- VSGNNIFQASZAOI-UHFFFAOYSA-L Calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 6
- 239000001639 calcium acetate Substances 0.000 claims description 6
- 235000011092 calcium acetate Nutrition 0.000 claims description 6
- 229960005147 calcium acetate Drugs 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- DJWUNCQRNNEAKC-UHFFFAOYSA-L Zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 235000010338 boric acid Nutrition 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 5
- 239000004328 sodium tetraborate Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L Copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 9
- 235000021003 saturated fats Nutrition 0.000 claims 4
- 239000000460 chlorine Substances 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- 239000010949 copper Substances 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 235000019197 fats Nutrition 0.000 claims 2
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004383 yellowing Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000005712 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 238000005461 lubrication Methods 0.000 description 2
- 230000003000 nontoxic Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 210000001736 Capillaries Anatomy 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000004301 light adaptation Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 230000002522 swelling Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Abstract
A kind of thermoplastic ethylene's base modified polyvinylalcohol resin, it is made of a effective amount of vinyl modified polyvinyl alcohol, plasticizer, soft water and processing aid, the vinyl modified polyvinyl alcohol is obtained through alcoholysis with after the unsaturated monomer copolymerization containing vinyl by vinyl acetate monomer, its alcoholysis degree is 80.0 99.9 (mol) %, the degree of polymerization is 1000~3000, and the modified amount of the unsaturated monomer containing vinyl is 0.1~20 (mol) %；The plasticizer is at least one of glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, and the processing aid is at least one of talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester.320 DEG C of decomposition temperature of thermoplastic ethylene's base modified polyvinylalcohol resin of 160 220 DEG C of melting temperature or more, water white transparency, non-yellowing, excellent quality.
Description
Technical field
The present invention relates to a kind of modified polyvinylalcohol resins, and in particular to a kind of thermoplastic ethylene Ji Gaixingjuyixichunshu
Fat and preparation method thereof.
Background technology
Polyvinyl alcohol (PVA) is a kind of function admirable, widely used high molecular material, since polyvinyl alcohol has polyhydroxy
The design feature of base, strong hydrogen bonding makes it have many excellent performances, is widely used in coating, adhesive, paper sizing agent
Equal fields.By polyvinyl alcohol resin be used to prepare film or proximate matter be current polyvinyl alcohol resin application new direction, by PVA systems
Standby film or proximate matter has the advantages that excellent resistance oxygen, oil resistance and not static electrification, not dust suction, intensity is high, and in certain item
There is water-soluble and biological degradability, therefore, the film or proximate matter prepared by polyvinyl alcohol is expected to substituting tradition packet under part
Package material prevents to play an important role in terms of white pollution.
But polyvinyl alcohol is crystalline polymer, contains great amount of hydroxy group in molecule, can form a large amount of intramolecular and divide
Hydrogen bond between son makes its fusing point be up to 200-240 DEG C, and decomposition temperature is low, 160 DEG C start dehydration, 200 DEG C start decompose, 220 DEG C
It decomposes completely, the fusing point and decomposition temperature of PVA is close, it is difficult to direct thermoplastic processing molding.
Current technology both domestic and external is to weaken polyvinyl alcohol point by being copolymerized or being added the method for plasticizer blending mostly
With intermolecular Hyarogen-bonding in sub, its fusing point is reduced, thermoplastic processing is made it have, to obtain melt-processable
Modified polyvinylalcohol resin or polyvinyl alcohol blending modified resin.The introducing of relatively large comonomer can effectively reduce polyethylene
Hyarogen-bonding in alcohol molecule, melting temperature and decomposition temperature are clearly separated, and such as EVOH resins, but modifying process is complicated, work
Industry difficulty is big.In existing polyvinyl alcohol production technology, a small amount of modified monomer is introduced in the course of the polymerization process, and melting temperature has
Declined, but still cannot independent thermoplastic processing.
Invention content
Present invention aims at provide a kind of thermoplastic ethylene's base modified polyvinylalcohol resin that quality is good.
Another object of the present invention is to provide the preparation method of above-mentioned thermoplastic ethylene's base modified polyvinylalcohol resin.
What the object of the invention was achieved through the following technical solutions, it is in parts by weight to be not particularly illustrated below：
A kind of thermoplastic ethylene's base modified polyvinylalcohol resin, it is characterised in that：It is by a effective amount of vinyl modified
Polyvinyl alcohol, plasticizer, soft water and processing aid composition, the vinyl modified polyvinyl alcohol be by vinyl acetate monomer with contain
It is obtained through alcoholysis after thering is the unsaturated monomer of vinyl to be copolymerized, alcoholysis degree is 80.0-99.9 (mol) %, the degree of polymerization is
1000~3000, the modified amount of the unsaturated monomer containing vinyl is 0.1~20 (mol) %；The plasticizer be glycerine,
At least one of polyethylene glycol, two tricaprylate of triethylene glycol, the processing aid be talcum powder, silica, erucyl amide,
At least one of saturated aliphatic dicarboxylic acids ester.
The unsaturated monomer containing vinyl refers to containing more than one C=C in vinyl modified polyvinyl alcohol of the present invention
Alkene of unsaturated double-bond, such as ethylene, propylene, butylene, pentadiene etc..Above-mentioned saturated aliphatic dicarboxylic acids ester is by containing 2-
30 C atoms, the aliphatic acid of 1-5 COOH group with contain 1-10 C atom, made of the fatty acid of 1-5 OH group,
The saturated aliphatic dicarboxylic acids ester series material is commercial product, such as the trade mark of Hangzhou Jin Cheng auxiliary agents Co., Ltd production is
The saturated aliphatic dicarboxylic acids ester of G32, G36, G60 etc..Above-mentioned glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, talcum
Powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester, ethylene, propylene, butylene, pentadiene are known, commercially available production
Product.
Plasticizer of the present invention effectively reduces the melt processing temperature of modified PVA；On the one hand soft water of the present invention plays plasticizer
Effect, on the other hand rise swelling action, allow PVA molecules preferably to absorb plasticizer and processing aid.Processing aid of the present invention
It is good with PVA compatibilities.Above-mentioned thermoplastic ethylene's base modified polyvinylalcohol resin melting temperature is effectively reduced, can be used for melting
Thermoplastic processing is molded, and decomposition temperature is also improved, significantly improves product quality；Meanwhile entire Plasticising system lubricity is good,
Placement is not easy the moisture absorption, adhesion.
In order to further improve the melt-processable of thermoplastic ethylene's base modified polyvinylalcohol resin of the present invention, improve tree
Fat quality, it is preferable that above-mentioned resin is by 50-85 parts of above-mentioned vinyl modified polyvinyl alcohol, 5-40 parts of above-mentioned plasticizer, 5-
20 parts of above-mentioned soft water and 0.1-15 part above-mentioned processing aid compositions.
Specifically, the vinyl modified polyvinyl alcohol be by vinyl acetate monomer and vinyl monomer or propylene monomer or
It is obtained through alcoholysis after butene monomers copolymerization, alcoholysis degree is 80.0-99.9 (mol) %, the degree of polymerization is 1000~3000, ethylene
The modified amount of monomer or propylene monomer or butene monomers is 0.1~20 (mol) %；The plasticizer is mass ratio 3-6：0-2：5-
6 glycerine, polyethylene glycol, two tricaprylate of triethylene glycol composition, the processing aid are mass ratio 2-4：0-3：1-4：2-4's
Talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester composition.
In order to further improve the decomposition temperature of obtained thermoplastic ethylene's base modified polyvinylalcohol resin, to improve
Its quality, while its weatherability is improved, it is further preferred that a kind of thermoplastic ethylene's base modified polyvinylalcohol resin, feature
It is：It is made by raw material of a effective amount of vinyl modified polyvinyl alcohol, plasticizer, soft water, processing aid and crosslinking agent,
The vinyl modified polyvinyl alcohol is obtained through alcoholysis with after the unsaturated monomer copolymerization containing vinyl by vinyl acetate monomer
, alcoholysis degree is 80.0-99.9 (mol) %, the degree of polymerization is 1000~3000, and the unsaturated monomer containing vinyl changes
Property amount be 0.1~20 (mol) %；The plasticizer is at least one in glycerine, polyethylene glycol, two tricaprylate of triethylene glycol
Kind, the processing aid is talcum powder, silica, erucyl amide, at least one of saturated aliphatic dicarboxylic acids ester, described
Crosslinking agent is at least one of calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid, borax.
In order to preferably improve the quality of thermoplastic ethylene's base modified polyvinylalcohol resin, it is highly preferred that above-mentioned resin with
50-85 parts of above-mentioned vinyl modified polyvinyl alcohol, 5-40 parts of above-mentioned plasticizer, 5-20 parts of above-mentioned soft water, 0.1-15 parts
Above-mentioned processing aid and above-mentioned 0.1-5 parts of crosslinking agent are made for raw material.
Preferably say, the vinyl modified polyvinyl alcohol be by vinyl acetate monomer and vinyl monomer or propylene monomer or
It is obtained through alcoholysis after butene monomers copolymerization, alcoholysis degree is 80.0-99.9 (mol) %, the degree of polymerization is 1000~3000, ethylene
The modified amount of monomer or propylene monomer or butene monomers is 0.1~20 (mol) %；The plasticizer is mass ratio 3-6：0-2：5-
6 glycerine, polyethylene glycol, two tricaprylate of triethylene glycol composition, the processing aid are mass ratio 2-4：0-3：1-4：2-4's
Talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester composition, the crosslinking agent are mass ratio 1-3：2-4：0-
3：1-3：3-5：Calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid and the borax of 5-6.
Above-mentioned thermoplastic ethylene's base modified polyvinylalcohol resin can be any shape, such as graininess, cylindrical, circular cone
The bodily form, square build, cuboid-type, sheet, disc-shaped, S shapes, V-arrangement, hollow circuit cylinder build, the hollow cone bodily form, hollow square
At least any shape in build, hollow cuboid-type.
The above-mentioned preferably a diameter of 0.5-15mm of thermoplastic ethylene's base modified polyvinylalcohol resin, the cylinder of high 0.5-15mm
Body.
The preparation method of above-mentioned thermoplastic ethylene's base modified polyvinylalcohol resin, prepares according to the following steps：
(1) by 50-85 parts of above-mentioned vinyl modified polyvinyl alcohol, 5-40 parts of above-mentioned plasticizer, 5-20 parts of soft water,
0.1-15 parts of above-mentioned processing aids are uniformly mixed and are warming up to 30-90 DEG C, holding 1/6-10 hours；
(2) step (1) described material is delivered in screw extruder, in 120-220 DEG C of temperature, melting extrusion is cooling
To 20-40 DEG C, thermoplastic ethylene's base modified polyvinylalcohol resin of the present invention is made through pelleter pelletizing moulding.
When containing crosslinking agent in blending constituent described in above-mentioned (1) step, 0.1-5 parts of above-mentioned crosslinking agent mixing are also added
Uniformly.
The hybrid mode of material preferably uses agitating mode to mix in above-mentioned (1) step.
The preferred single screw extrusion machine of screw extruder in above-mentioned (2) step.
Screw extruder is divided into feeding part and screw rod melting extrusion part, wherein feeding part in above-mentioned (2) step
Feeding bin use with blender feeding bin.
Thermoplastic ethylene's base modified polyvinylalcohol resin of the present invention can pass through blowing, extrusion molding, calendering, melting extrusion-
Thermoplastic ethylene's base modified polyvinylalcohol resin is prepared film forming or proximate matter by the modes such as biaxial tension, melting extrusion-curtain coating, into one
Step is for each field packaging, toy.
Compared with prior art, the present invention having the positive effect that：
1, the melting temperature of thermoplastic ethylene's base modified polyvinylalcohol resin of the present invention is reduced to 160-220 DEG C, makes this hair
Bright thermoplastic ethylene's base modified polyvinylalcohol resin smoothly realizes various thermoplastic processings.
2 at the same thermoplastic ethylene's base modified polyvinylalcohol resin of the present invention decomposition temperature be increased to 320 DEG C -400 DEG C,
It is water white transparency, non-yellowing；Melt index is 1-20g/10min (190 DEG C/2.16~10kg), and processing fluidity is excellent, mouldability
It is good；Resin crystallization degree is (30.0%-60.0%), is used for the excellent in mechanical performance of following process.Using thermoplasticity second of the present invention
Film or proximate matter intensity prepared by alkenyl modified polyvinylalcohol resin is high, dries rear film or proximate matter intensity reaches 60-150MPa；Change
Property resin lubrication is good, nonhygroscopic, adhesion, while place 1 year appearance, color will not change；Non-toxic of the present invention,
It can degrade under certain conditions, be conducive to environmental protection.
The present invention relates to test method it is as follows：
1, the test of melting temperature and decomposition temperature：It is characterized using heat analysis (DSC) curve, crucible used is that high pressure is stainless
Steel crucible is tested in nitrogen atmosphere, heating rate：10 DEG C/min, Range of measuring temp：- 250 DEG C of room temperature.
2, the test of melt index：According to the resin flow behavior of the different PVA trades mark, using fusion index instrument, a constant temperature
Under degree, constant pressure, the mass value that plastic melt flows through standard capillary in 10min, unit g/10min are measured.This test
Method set temperature：160 DEG C~220 DEG C；Pressure：2.16kg~10kg.
3, inflation film stretching strength determination：With reference to standard GB/T 13022-91 stretched plastic film method for testing performances
It is tested.
4, it is molded batten stretching strength determination：It is tested with reference to standard GB/T 1040-79 plastic tensile test methods.
Specific implementation mode
The present invention is specifically described below by embodiment, it is necessary to which indicated herein to be, the present embodiment is served only for
Invention is further explained, should not be understood as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations are made to the present invention according to the above, still fall within protection scope of the present invention.Following reality
It applies in example, unless otherwise, all % and number are all as unit of mass percentage, mass weight.
Embodiment 1：By 63 parts of vinyl modified polyvinyl alcohol, (the vinyl modified polyvinyl alcohol is by vinyl acetate monomer
It is obtained through alcoholysis after being copolymerized with butene monomers, alcoholysis degree is 90 (mol) %, the degree of polymerization 2000, the modification of butene monomers
Amount is 0.1~1 (mol) %), 12 parts of glycerine, 10 parts of two tricaprylates of triethylene glycol, 12 parts of soft water, 7 parts of erucyl amides, 2 parts it is full
It is uniformly mixed under stirring with aliphatic dicarboxylic acid ester G60, is heated while stirring at a temperature of 45 DEG C, stop adding after 2h
Heat.Then material is added in the feed bin with stirring, is delivered to material in screw extruder automatically using screw rod, keep spiral shell
160 DEG C of bar temperature, melting extrusion in atmospheric conditions, then material is cooled to 30 DEG C, thermoplastic is made through pelleter pelletizing moulding
Sex ethylene base modified polyvinylalcohol resin.
The decomposition temperature of gained resin is 365 DEG C, water white transparency, non-yellowing, 175 DEG C of melting temperature, melt index 6g/
10min (190 DEG C/2.16~10kg), resin is graininess.
Embodiment 2：By 52 parts of vinyl modified polyvinyl alcohol, (the vinyl modified polyvinyl alcohol is by vinyl acetate monomer
It is obtained through alcoholysis after being copolymerized with propylene monomer, alcoholysis degree is 80.0 (mol) %, the degree of polymerization 3000, and propylene monomer changes
Property amount be 16~20 (mol) %), 3 parts of glycerine, 2 parts of polyethylene glycol, 1 part of two tricaprylate of triethylene glycol, 7 parts of soft water, 0.5 part
Silica mixes, and is uniformly mixed under stirring, is heated while stirring at a temperature of 30 DEG C, stops heating after ten minutes.
Then material is added in the feed bin with stirring, is delivered to material in single screw extrusion machine automatically using screw rod, keep spiral shell
180 DEG C of bar temperature, the melting extrusion under 0.01MPa (gauge pressure) pressure condition, then material is cooled to 40 DEG C, through pelleter pelletizing
Thermoplastic ethylene's base modified polyvinylalcohol resin is made in moulding.
The decomposition temperature of gained resin is 325 DEG C, 170 DEG C of melting temperature, melt index 10g/10min (190 DEG C/2.16
~10kg), resin is diameter 2.0mm, the cylinder of high 0.5mm.
Embodiment 3：By 83 parts of vinyl modified conventional polyvinyl alcohols, (the vinyl modified polyvinyl alcohol is by vinyl acetate
It is obtained through alcoholysis after monomer and fluoride monomers, alcoholysis degree is 99.9 (mol) %, the degree of polymerization 1000, vinyl monomer
Modified amount be 8~12 (mol) %), 38 parts of two tricaprylates of triethylene glycol, 20 parts of soft water, 11 parts of talcum powder, 4 parts of erucyl amides
Mixing is uniformly mixed under stirring, is heated while stirring at a temperature of 90 DEG C, stops heating after 6h.Then material is added
Enter in the feed bin with stirring, be delivered to material in single screw extrusion machine automatically using single screw rod, keeps extruder temperature 190
DEG C, melting extrusion in atmospheric conditions, then material is cooled to 20 DEG C, thermoplastic ethylene's base, which is made, through pelleter pelletizing moulding changes
Property polyvinyl alcohol resin.
The decomposition temperature of gained resin is 390 DEG C, 180 DEG C of melting temperature, melt index 12g/10min (190 DEG C/2.16
~10kg), resin is square shape.
Embodiment 4：By 85 parts of vinyl modified polyvinyl alcohol, (the vinyl modified polyvinyl alcohol is by vinyl acetate monomer
With obtained through alcoholysis after fluoride monomers, alcoholysis degree is 85.0 (mol) %, the degree of polymerization 1600, the modified of ethylene is measured
For 1~3 (mol) %), 5 parts of mass ratioes be 5：4 two tricaprylate of glycerine and triethylene glycol, 14 parts of soft water, 6 parts of mass ratioes are
3：5：1 talcum powder, silica and saturated aliphatic dicarboxylic acids ester G36,2 parts of crosslinking agent calcium acetate mixing, in stirring
It is lower to be uniformly mixed, it is heated while stirring at a temperature of 90 DEG C, stops heating after 6 hours.Then material is added with stirring
In feed bin, material is delivered in single screw extrusion machine automatically using twin-screw, 180 DEG C of extruder temperature is kept, in condition of normal pressure
Lower melting extrusion, then material is cooled to 30 DEG C, thermoplastic ethylene Ji Gaixingjuyixichunshu is made through pelleter pelletizing moulding
Fat.
The decomposition temperature of gained thermoplastic ethylene's base modified polyvinylalcohol resin is 380 DEG C, water white transparency, non-yellowing, is melted
Melt 185 DEG C of temperature, melt index 5.5g/10min (190 DEG C/2.16~10kg).
Embodiment 5-9：A kind of thermoplastic ethylene's base modified polyvinylalcohol resin presses following material and technique, remaining is the same as implementing
Example 4.
The thermoplastic ethylene's base modified polyvinylalcohol resin obtained by embodiment 5-9,160-220 DEG C of melting temperature, thermoplastic
The decomposition temperature of sex ethylene base modified polyvinylalcohol resin is 320 DEG C -400 DEG C, water white transparency, non-yellowing；Melt index is 1-
20g/10min (190 DEG C/2.16~10kg), processing fluidity is excellent, good moldability；Resin crystallization degree is 30.0%-
60.0%, it is used for the excellent in mechanical performance of following process, is prepared using thermoplastic ethylene's base modified polyvinylalcohol resin of the present invention
Film or proximate matter intensity it is high, dry rear film or proximate matter intensity reach 60-150MPa；Resin lubrication is good, it is nonhygroscopic, do not glue
Even, while 1 year appearance of placement, color will not change；Non-toxic of the present invention can degrade, be conducive under certain conditions
Environmental protection.
Claims (18)
1. a kind of thermoplastic ethylene's base modified polyvinylalcohol resin, it is characterised in that：It is by the 50-85 parts of poly- second of vinyl modified
Enol, 5-40 part plasticizer, 5-20 parts of soft water and 0.1-15 parts of processing aid compositions, are in parts by weight, the vinyl changes
Property polyvinyl alcohol be the alcoholysis degree by being obtained through alcoholysis after vinyl acetate monomer and the unsaturated monomer copolymerization containing vinyl
For 80.0-99.9 (mol) %, degree of polymerization 1000-3000, the modified amount of the unsaturated monomer containing vinyl is 0.1-20
(mol)%；The plasticizer is at least one of glycerine, polyethylene glycol, two tricaprylate of triethylene glycol, the processing aid
For at least one of talcum powder, silica, erucyl amide, saturated aliphatic dicarboxylic acids ester.
2. thermoplastic ethylene's base modified polyvinylalcohol resin as described in claim 1, it is characterised in that：The representative examples of saturated aliphatic
Dicarboxylic ester is G32, G36 or G60.
3. thermoplastic ethylene's base modified polyvinylalcohol resin as described in claim 1, it is characterised in that：The vinyl modified
Polyvinyl alcohol is the alcohol by being obtained through alcoholysis after vinyl acetate monomer and vinyl monomer or propylene monomer or butene monomers copolymerization
Xie Du is the modified amount of 80.0-99.9 (mol) %, degree of polymerization 1000-3000, vinyl monomer or propylene monomer or butene monomers
For 0.1-20 (mol) %；The plasticizer is mass ratio 3-6：0-2：Glycerine, polyethylene glycol, two isooctyl acid of triethylene glycol of 5-6
Ester forms, and the processing aid is mass ratio 2-4：0-3：1-4：Talcum powder, silica, erucyl amide, the saturated fat of 2-4
Race's dicarboxylic ester composition.
4. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 2, it is characterised in that：The vinyl modified
Polyvinyl alcohol is the alcohol by being obtained through alcoholysis after vinyl acetate monomer and vinyl monomer or propylene monomer or butene monomers copolymerization
Xie Du is the modified amount of 80.0-99.9 (mol) %, degree of polymerization 1000-3000, vinyl monomer or propylene monomer or butene monomers
For 0.1-20 (mol) %；The plasticizer is mass ratio 3-6：0-2：Glycerine, polyethylene glycol, two isooctyl acid of triethylene glycol of 5-6
Ester forms, and the processing aid is mass ratio 2-4：0-3：1-4：Talcum powder, silica, erucyl amide, the saturated fat of 2-4
Race's dicarboxylic ester composition.
5. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 2, it is characterised in that：The resin is particle
Shape, cylindrical, cone shape, the square bodily form, cuboid, sheet, S shapes, V-arrangement, the hollow circuit cylinder bodily form, hollow cone
Shape, the hollow square bodily form or hollow cuboid.
6. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 5, it is characterised in that：The resin is disk
Shape.
7. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 2, it is characterised in that：The thermoplastic ethylene
Base modified polyvinylalcohol resin is the cylinder of a diameter of 0.5-15mm, high 0.5-15mm.
8. a kind of thermoplastic ethylene's base modified polyvinylalcohol resin, it is characterised in that：It is with the 50-85 parts of poly- second of vinyl modified
Enol, 5-40 part plasticizer, 5-20 parts of soft water, 0.1-15 parts of processing aids and 0.1-5 parts of crosslinking agents are made for raw material, with weight
Part meter is measured, the vinyl modified polyvinyl alcohol is by being passed through after vinyl acetate monomer and the unsaturated monomer copolymerization containing vinyl
What alcoholysis obtained, alcoholysis degree is 80.0-99.9 (mol) %, degree of polymerization 1000-3000, the unsaturated monomer containing vinyl
Modified amount be 0.1-20 (mol) %；The plasticizer is at least one in glycerine, polyethylene glycol, two tricaprylate of triethylene glycol
Kind, the processing aid is talcum powder, silica, erucyl amide, at least one of saturated aliphatic dicarboxylic acids ester, described
Crosslinking agent is at least one of calcium acetate, zinc acetate, copper chloride, zinc chloride, boric acid, borax.
9. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 8, it is characterised in that：The representative examples of saturated aliphatic two
Carboxylate is G32, G36 or G60.
10. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 8, it is characterised in that：The vinyl changes
Property polyvinyl alcohol be by being obtained through alcoholysis after vinyl acetate monomer and vinyl monomer or propylene monomer or butene monomers copolymerization,
Alcoholysis degree is the modification of 80.0-99.9 (mol) %, degree of polymerization 1000-3000, vinyl monomer or propylene monomer or butene monomers
Amount is 0.1-20 (mol) %；The plasticizer is mass ratio 3-6：0-2：Glycerine, polyethylene glycol, the triethylene glycol two of 5-6 is different pungent
Acid esters forms, and the processing aid is mass ratio 2-4：0-3：1-4：Talcum powder, silica, erucyl amide, the saturated fat of 2-4
Fat race dicarboxylic ester composition, the crosslinking agent are mass ratio 1-3：2-4：0-3：1-3：3-5：Calcium acetate, zinc acetate, the chlorine of 5-6
Change copper, zinc chloride, boric acid and borax.
11. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 9, it is characterised in that：The vinyl changes
Property polyvinyl alcohol be by being obtained through alcoholysis after vinyl acetate monomer and vinyl monomer or propylene monomer or butene monomers copolymerization,
Alcoholysis degree is the modification of 80.0-99.9 (mol) %, degree of polymerization 1000-3000, vinyl monomer or propylene monomer or butene monomers
Amount is 0.1-20 (mol) %；The plasticizer is mass ratio 3-6：0-2：Glycerine, polyethylene glycol, the triethylene glycol two of 5-6 is different pungent
Acid esters forms, and the processing aid is mass ratio 2-4：0-3：1-4：Talcum powder, silica, erucyl amide, the saturated fat of 2-4
Fat race dicarboxylic ester composition, the crosslinking agent are mass ratio 1-3：2-4：0-3：1-3：3-5：Calcium acetate, zinc acetate, the chlorine of 5-6
Change copper, zinc chloride, boric acid and borax.
12. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 9, it is characterised in that：The resin is
Granular, cylindrical, cone shape, the square bodily form, cuboid, sheet, disc-shaped, S shapes, V-arrangement, the hollow circuit cylinder bodily form, in
Empty cone shape, the hollow square bodily form or hollow cuboid.
13. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 12, it is characterised in that：The resin is circle
Sheet.
14. thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 9, it is characterised in that：The thermoplasticity second
Alkenyl modified polyvinylalcohol resin is the cylinder of a diameter of 0.5-15mm, high 0.5-15mm.
15. the preparation method of thermoplastic ethylene's base modified polyvinylalcohol resin, feature exist as described in claim any one of 1-7
In preparing according to the following steps：
（1）The vinyl modified polyvinyl alcohol, plasticizer, soft water, processing aid are uniformly mixed and are warming up to 30-90
DEG C, it is kept for 1/6-10 hours；
（2）By step（1）Resulting material is delivered in screw extruder, in 120-220 DEG C of melting extrusion, is cooled to 20-40 DEG C,
Thermoplastic ethylene's base modified polyvinylalcohol resin is made through pelleter pelletizing moulding.
16. the preparation method of thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 15, it is characterised in that：It is described
Step（1）Middle hybrid mode uses and is stirred mode；The step（2）Middle screw extruder uses single screw extrusion machine；Institute
It includes feeding part and screw rod melting extrusion part to state single screw extrusion machine, and the wherein feeding bin of feeding part is used with stirring
The feeding bin of device.
17. the preparation method of thermoplastic ethylene's base modified polyvinylalcohol resin, feature as described in claim any one of 8-14
It is, prepares according to the following steps：
（1）The vinyl modified polyvinyl alcohol, plasticizer, soft water, processing aid, crosslinking agent are uniformly mixed and are warming up to
It 30-90 DEG C, is kept for 1/6-10 hours；
（2）By step（1）Resulting material is delivered in screw extruder, in 120-220 DEG C of melting extrusion, is cooled to 20-40 DEG C,
Thermoplastic ethylene's base modified polyvinylalcohol resin is made through pelleter pelletizing moulding.
18. the preparation method of thermoplastic ethylene's base modified polyvinylalcohol resin as claimed in claim 17, it is characterised in that：It is described
Step（1）Middle hybrid mode uses and is stirred mode；The step（2）Middle screw extruder uses single screw extrusion machine；Institute
It includes feeding part and screw rod melting extrusion part to state single screw extrusion machine, and the wherein feeding bin of feeding part is used with stirring
The feeding bin of device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410515857.7A CN105440523B (en) | 2014-09-29 | A kind of thermoplastic modification polyvinyl alcohol resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410515857.7A CN105440523B (en) | 2014-09-29 | A kind of thermoplastic modification polyvinyl alcohol resin and preparation method thereof |
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| Publication Number | Publication Date |
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| CN105440523B true CN105440523B (en) | 2018-08-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391598A (en) * | 2011-09-07 | 2012-03-28 | 北京工商大学 | Polyvinyl alcohol material and production method thereof |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391598A (en) * | 2011-09-07 | 2012-03-28 | 北京工商大学 | Polyvinyl alcohol material and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 改善PVA熔融加性能的研究现状;侯双燕等;《合成纤维》;20090525;第38卷(第5期);第1-3页 * |
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