CN106832067A - A kind of preparation method of ionic polyvinyl butyral resin - Google Patents
A kind of preparation method of ionic polyvinyl butyral resin Download PDFInfo
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- CN106832067A CN106832067A CN201611192065.6A CN201611192065A CN106832067A CN 106832067 A CN106832067 A CN 106832067A CN 201611192065 A CN201611192065 A CN 201611192065A CN 106832067 A CN106832067 A CN 106832067A
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- China
- Prior art keywords
- ionic
- polyvinyl butyral
- butyral resin
- reactor
- ionic polyvinyl
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 title claims abstract description 136
- 229920005989 resin Polymers 0.000 title claims abstract description 108
- 239000011347 resin Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 126
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000000203 mixture Substances 0.000 claims abstract description 89
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 62
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000178 monomer Substances 0.000 claims abstract description 47
- -1 aldehyde compound Chemical class 0.000 claims abstract description 45
- 239000007787 solid Substances 0.000 claims abstract description 45
- 238000010792 warming Methods 0.000 claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 238000005406 washing Methods 0.000 claims abstract description 26
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 238000006073 displacement reaction Methods 0.000 claims abstract description 23
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 69
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 50
- 229940117958 vinyl acetate Drugs 0.000 claims description 50
- 230000015572 biosynthetic process Effects 0.000 claims description 45
- 238000003786 synthesis reaction Methods 0.000 claims description 45
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 30
- 125000003010 ionic group Chemical group 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000007334 copolymerization reaction Methods 0.000 claims description 24
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 24
- 238000013019 agitation Methods 0.000 claims description 22
- 239000012429 reaction media Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006386 neutralization reaction Methods 0.000 claims description 20
- 150000001299 aldehydes Chemical class 0.000 claims description 19
- 238000003860 storage Methods 0.000 claims description 19
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 18
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 18
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims description 18
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 9
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 9
- 229940100595 phenylacetaldehyde Drugs 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 3
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000005336 safety glass Substances 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 description 63
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 26
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 26
- 239000000047 product Substances 0.000 description 23
- 239000007788 liquid Substances 0.000 description 21
- 229920002554 vinyl polymer Polymers 0.000 description 20
- 238000000926 separation method Methods 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 239000007790 solid phase Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000008187 granular material Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 125000005395 methacrylic acid group Chemical group 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 3
- 150000002085 enols Chemical class 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000005340 laminated glass Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- SSKNCQWPZQCABD-UHFFFAOYSA-N 2-[2-[2-(2-heptanoyloxyethoxy)ethoxy]ethoxy]ethyl heptanoate Chemical compound CCCCCCC(=O)OCCOCCOCCOCCOC(=O)CCCCCC SSKNCQWPZQCABD-UHFFFAOYSA-N 0.000 description 1
- SJVGFKBLUYAEOK-SFHVURJKSA-N 6-[4-[(3S)-3-(3,5-difluorophenyl)-3,4-dihydropyrazole-2-carbonyl]piperidin-1-yl]pyrimidine-4-carbonitrile Chemical compound FC=1C=C(C=C(C=1)F)[C@@H]1CC=NN1C(=O)C1CCN(CC1)C1=CC(=NC=N1)C#N SJVGFKBLUYAEOK-SFHVURJKSA-N 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of preparation method of ionic polyvinyl butyral resin, it is characterized in that：After the air gone out in reactor A with nitrogen displacement, add mix monomer, methyl alcohol and azodiisobutyronitrile, 55~70 DEG C are warming up to react 4~5 hours, 30 DEG C are cooled to, sodium hydrate aqueous solution, alcoholysis 4~5 hours is added, it is neutralized to neutrality, filtering, solids is washed with methyl alcohol, dried, and ionic polyvinyl resin is obtained；By in ionic polyvinyl resin addition reactor B, the aqueous solution is dissolved and is made at 95 DEG C, cool to 15~32 DEG C, stirring is lower to add aldehyde compound and hydrochloric acid, be warming up to 55 DEG C reaction 5~7 hours after, 35 DEG C of filterings are cooled to, by solids washing, are dried, that is, ionic polyvinyl butyral resin is obtained.Obtained ionic polyvinyl butyral resin of the invention has rigidity higher, is particularly suitable for high rigidity, the manufacture of the structure safety glass product of high intensity.
Description
Technical field
The invention belongs to the preparation of organic high molecular compound, it is related to a kind of ionic polyvinyl butyral (English name
Referred to as Ionomeric Polyvinyl Butyral, abbreviation or referred to as IPVB) resin synthetic method, the present invention is obtained
Ionic polyvinyl butyral resin has rigidity higher, is particularly well-suited to the structure safety glass of high rigidity, high intensity
The manufacture of product.
Background technology
Polyvinyl butyral film (abbreviation PVB films) has good translucency, sound-proofing, ageing-resistant energy and bonding
Property, it has been always building, main force's material of automotive safety laminated glass from last century since the forties emerges.It is main in automotive field
Automobile front windshield being applied to, when there is contingency by self-deformation apparatus with shock absorbing, on the one hand can be avoided
Foreign matter is penetrated and injures occupant, is on the other hand prevented occupant from going out front window and is caused more major injury.It is main in building field
It is applied to skyscraper glass, glass curtain wall, bulletproof glass, corridor cover plate etc..Although excellent performance, each manufacturer is not
Abandon to the modified upgrading of PVB products, this is not enough mainly due to the rigidity of PVB materials, and support cannot be played after glass breaking
Effect, easily causes structure and collapses, and this is showed in transparent roofs, transparent corridor, the application of large glass curtain wall particularly dashes forward
Go out.It is a kind of ionic polymerization that the sandwich material of high rigidity has Du Pont SGP and head promise Saflex DG, SGP films in the market
Thing film, causes that the material room temperature is rigidly good because ionic bond forms reversible crosslink system, and with good workability.
In the prior art, the patent US5030688 and US4968745 of Shou Nuo companies disclose the synthesis side of ionic PVB
Method, is the acetalation stage in polyvinyl alcohol, with aldehyde and hydroxyl reaction containing acidic-group, ionic group is introduced into PVB molecules
IPVB resins are formed in chain.Ionic groups are introduced PVB by the program by the way of graft modification, and raw material used is not easy to obtain
Arrive, price is higher, in addition, grafting rate is low, wastage of material is more；And with the PVB films prepared by it in rigidity, caking property, transparent
Property, weatherability have some shortcomings, can't well meet the high performance requirements in market, and practicality is poor.
The content of the invention
The purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, there is provided a kind of ionic polyvinyl butyral
The preparation method of resin.The present invention is especially protruded with ionic comonomer and the synthetic route of non-ionic monomer copolymerization, prepared rigidity
Ionic polyvinyl butyral (abbreviation IPVB) resin, so as to efficiently solve polyvinyl butyral resin in the prior art
(PVB) problem of the poor performance such as the rigidity of institute's generally existing, caking property, the transparency, weatherability technology.
Present disclosure is：A kind of preparation method of ionic polyvinyl butyral (abbreviation IPVB) resin, it is special
Levy is that step is：
A, synthesis ionic polyvinyl resin：The air in reactor A first is removed with nitrogen displacement, then to reactor A
300~500 mass parts mix monomers of middle addition, 1000 mass parts Methanols and 0.1~0.5 mass parts azodiisobutyronitrile, stirring
And 55~70 DEG C are warming up to, copolymerization is cooled to 30 DEG C after 4~5 hours, then to 170~195 matter of addition in reactor A
Amount part mass percent concentration is 15% sodium hydrate aqueous solution, after carrying out alcoholysis 4~5 hours, is neutralized with (appropriate) acetic acid
Reaction medium is filtered (carrying out separation of solid and liquid) to neutrality, and solids is washed 3~6 times with (appropriate) methyl alcohol, then by solids (i.e.
Filter cake) dry after, as obtained ionic polyvinyl resin (pellet)；
The mix monomer is the mixture of vinylacetate and ionic comonomer；
The ionic comonomer is the ionic acid compounds containing unsaturated double-bond and the ion containing unsaturated double-bond
One or more mixture in type salt compounds；
B, synthesis ionic polyvinyl butyral：100 mass parts ionic polyvinyl resins are added into reactor B
In, dissolved at 95 DEG C and be configured to the ionic polyvinyl resin aqueous solution that mass percent concentration is 6~15%, then
After cooling to 15~32 DEG C, 50~67 mass parts aldehyde compounds and 6~20 mass parts hydrochloric acid (matter of hydrochloric acid are added under agitation
Amount part consumption with HCl be hydrogen chloride mass parts calculate) mixed, be warming up to 55 DEG C reaction 5~7 hours after, be cooled to 35
DEG C filtering, by solids (i.e. filter cake) 500 mass parts water washing 4~6 times every time, then by solids (i.e. filter cake) drying after,
As obtained ionic polyvinyl butyral resin (finished product)；
The aldehyde compound be butyraldehyde with C5~C8 aliphatic aldehydes compound, C5~C8 aromatic aldehyde compounds in extremely
A kind of the constituted mixture of few mixing.
In present disclosure：Mix monomer described in step a is the mixture of vinylacetate and ionic comonomer, its
In：The mole percentage of vinylacetate is that the mole percentage of 70%~98%, ionic comonomer is 2%~30%.
In present disclosure：Mix monomer described in step a is the mixture of vinylacetate and ionic comonomer, its
In：The mole percentage 5%~15% of the mole percentage 85%~95%, ionic comonomer of vinylacetate.
In present disclosure：Ionic comonomer described in step a can be, but not limited to be acrylic acid, methacrylic acid,
One kind in the salt of vinyl sulfonic acid, styrene sulfonic acid, allyl sulphonic acid, methacrylic sulfonic acid and aforesaid compound or or
Two or more mixtures.
In present disclosure：Aldehyde compound described in step b can be the fourth that mass percent is 85%~100%
Aldehyde and mass percent be in 0~15% valeral, hexanal, enanthaldehyde, octanal, benzaldehyde, phenylacetaldehyde any one or two kinds of with
The constituted mixture of upper mixing.
In present disclosure：Contain remaining acetic acid in the structure of obtained ionic polyvinyl resin described in step a
Root, three kinds of groups of ionic groups and vinyl alcohol, wherein：The mole percentage of acetate is 0.05%~0.5%, ion
The mole percentage of type group is that 2%~25%, remaining (i.e. surplus) is vinyl alcohol.
In present disclosure：The molecule knot of obtained ionic polyvinyl butyral (abbreviation IPVB) described in step b
Structure is made up of acetal radical, vinyl alcohol, ionic groups and acetate, and the mole degree of wherein ionic groups is
2%~29%.
In present disclosure：The obtained ionic polyvinyl butyral (abbreviation IPVB) described in step b it is flat
Average molecular weight is 60000~180000,65~81 DEG C of glass transition temperature, storage modulus (at 25 DEG C) 2.36 × 106~
6.98×106G ＇/Pa, storage modulus (at 40 DEG C) 3.57 × 105~7.33 × 105G ＇/Pa, storage modulus (at 60 DEG C) 4.45
×105~7.46 × 105G ＇/Pa, storage modulus (at 160 DEG C) 3.29 × 104~7.10 × 104G ＇/Pa.
Compared with prior art, the present invention has following features and beneficial effect：
(1) present invention obtains middle precursor copolymer, middle precursor copolymer using ionic comonomer and Polymerization of Vac
Ionic polyvinyl is obtained by alcoholysis, ionic polyvinyl obtains ionic polyvinyl contracting fourth by acetalation
Aldehyde (abbreviation IPVB), preparation process is simple；
(2) present invention is using the high polymer ionic polyvinyl containing ionic bond in the prepared strand of ionic compound
Butyral resin, using the monomer containing ion center and non-ionic monomer copolymerization, to the non-ionic polymeric containing active group
Thing carries out the modes such as graft modification, and ionic bond is introduced in strand, obtained ionic polyvinyl butyral resin is existed
Under room temperature state, because of Ionomer ionic group " aggregation " characteristic, reversible crosslink area is formed, for material provides enough firm
Property, and in a heated state, reversible crosslink " can be also dismissed ", so that material shows as thermoplasticity, so as to obtain a kind of property
Exsertile polyvinyl butyral resin thermoplastic；Monomer used of the invention is easy to get, low cost, resin structure design and performance
Regulation and control are flexible；
(3) using the present invention, can be obtained with excellent rigidity, caking property, the transparency, weatherability laminated glass-use glue
Piece；Obtained ionic polyvinyl butyral (abbreviation IPVB) resin compared with conventional polyvinyl butyral (PVB), institute
The film being made has rigidity higher, and its key performance glass transition temperature (identical molecular weight condition) is by the 58 of comparative example
DEG C~66 DEG C bring up to 65 DEG C~81 DEG C of embodiment；Storage modulus (at 25 DEG C) is by the 1.12 × 10 of comparative example6~3.46 ×
106G ＇/Pa brings up to the 2.36 × 10 of embodiment6~6.98 × 106G ＇/Pa, storage modulus (at 40 DEG C) is by the 2.31 of comparative example
×105~4.76 × 105G ＇/Pa brings up to the 3.57 × 10 of embodiment5~7.33 × 105G ＇/Pa, storage modulus (at 60 DEG C)
By the 2.46 × 10 of comparative example5~4.29 × 105G ＇/Pa brings up to the 4.45 × 10 of embodiment5~7.46 × 105G ＇/Pa, storage
Energy modulus (at 160 DEG C) is by the 3.14 × 10 of comparative example4~5.63 × 104G ＇/Pa brings up to the 3.29 × 10 of embodiment4~
7.10×104G ＇/Pa, it is functional；
(4) using the obtained ionic polyvinyl butyral resin of the present invention, can be used to prepare high performance PVB glue
Piece, compared with common PVB films, more preferably, intensity is higher for its rigidity, is particularly well-suited to choose hollow structure glass, large-area glass curtain
The fields such as wall, bulletproof glass；
(5) preparation method of ionic polyvinyl butyral resin of the present invention there are no record and the report of any document
Road；Preparation section of the present invention is easy, and easily operation, practical.
Specific embodiment
The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes according to the content of the invention described above to the present invention
It is whole, still fall within protection scope of the present invention.
Embodiment 1：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 350 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：PAA=94：6), 1000 ㎏ methyl alcohol and 0.5 ㎏ azodiisobutyronitriles, stir
60 DEG C are mixed and be warming up to, copolymerization is after 5 hours, be cooled to 30 DEG C, then to adding the hydrogen of 180 ㎏ 15%wt in reactor A
Sodium hydroxide solution, after carrying out alcoholysis 5 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carries out separation of solid and liquid, then with appropriate
Methyl alcohol washing solid phase is filtered afterwards for several times, dries its filter cake, and filter cake is obtained ionic polyvinyl resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction (i.e. mass percent, afterwards together) 6.5% at 95 DEG C, after then cooling to 21 DEG C,
Add 61 ㎏ aldehyde compounds and 7 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) to be reacted under agitation, be warming up to 55 DEG C of reactions
After 5 hours, 35 DEG C of filterings are cooled to, filter cake 500 ㎏ water every time is dried after washing 6 times, i.e., obtained ionic gathers
Vinyl butyral resin finished product.
Obtained polyvinyl butyral resin number-average molecular weight 90120, ionic groups molar fraction (mole percentage
It is than content, afterwards together) 7.1%.
Embodiment 2：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 400 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Styrene sulfonic acid=89：11), 1000 ㎏ methyl alcohol and the isobutyl of 0.5 ㎏ azos two
Nitrile, stirs and is warming up to 55 DEG C, and copolymerization is after 4.5 hours, is cooled to 30 DEG C, then to adding 175 ㎏ 15% in reactor A
The sodium hydroxide solution of wt, after carrying out alcoholysis 4 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carries out separation of solid and liquid, then
Solid phase is washed with proper amount of methanol to filter afterwards for several times, its filter cake is dried, and filter cake is obtained ionic polyvinyl resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 8.0% at 95 DEG C, after then cooling to 22 DEG C, 60 ㎏ aldehyde is added under agitation
Class compound and 7 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 7 hours, are cooled to 35 DEG C
Filtering, filter cake 500 ㎏ water every time is dried after washing 6 times, i.e., obtained ionic polyvinyl butyral resin into
Product.
Obtained polyvinyl butyral resin number-average molecular weight 90260, ionic groups molar fraction is 13.5%.
Embodiment 3：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 470 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Methacrylic acid：Sodium vinyl sulfonate=86：5：9), 1000 ㎏ methyl alcohol and 0.4
㎏ azodiisobutyronitriles, stir and are warming up to 58 DEG C, and copolymerization is cooled to 30 DEG C, then add in reactor A after 5 hours
Enter the sodium hydroxide solution of 195 ㎏ 15%wt, after carrying out alcoholysis 4 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carry out
Separation of solid and liquid, then solid phase is washed with proper amount of methanol filter afterwards for several times, its filter cake is dried, filter cake is obtained ionic polyvinyl
Resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 6.5% at 95 DEG C, after then cooling to 20 DEG C, 65 ㎏ aldehyde is added under agitation
Class compound and 10 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 110070, ionic groups molar fraction is 16.2%.
Embodiment 4：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 420 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Methacrylic sulfonic acid=80：20), 1000 ㎏ methyl alcohol and 0.35 ㎏ azos two are different
Butyronitrile, stirs and is warming up to 63 DEG C, and copolymerization is after 4.5 hours, is cooled to 30 DEG C, then to adding 190 ㎏ in reactor A
The sodium hydroxide solution of 15%wt, after carrying out alcoholysis 4 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carries out solid-liquid point
From, then solid phase is washed with proper amount of methanol filter afterwards for several times, its filter cake is dried, filter cake is obtained ionic polyvinyl resin particle
Material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 9.1% at 95 DEG C, after then cooling to 15 DEG C, 62 ㎏ aldehyde is added under agitation
Class compound and 8 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 7 hours, are cooled to 35 DEG C
Filtering, filter cake 500 ㎏ water every time is dried after washing 6 times, i.e., obtained ionic polyvinyl butyral resin into
Product.
Obtained polyvinyl butyral resin number-average molecular weight 110420, ionic groups molar fraction is 23.6%.
Embodiment 5：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 390 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Vinyl sulfonic acid：Styrene sulfonic acid：Methacrylic sulfonic acid=82：8：8：2)、
1000 ㎏ methyl alcohol and 0.25 ㎏ azodiisobutyronitriles, stir and are warming up to 70 DEG C, and copolymerization is cooled to 30 DEG C after 5 hours,
Again to the sodium hydroxide solution that 185 ㎏ 15%wt are added in reactor A, after carrying out alcoholysis 4 hours, with appropriate acetic acid neutralization reaction
Medium carries out separation of solid and liquid to neutrality, then solid phase is washed with proper amount of methanol filters afterwards for several times, dries its filter cake, and filter cake is to be obtained
Ionic polyvinyl resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 14.2% at 95 DEG C, after then cooling to 25 DEG C, 59 ㎏ aldehyde is added under agitation
Class compound and 10 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 7 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 160330, ionic groups molar fraction is 18.7%.
Embodiment 6：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 470 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Sodium methacrylate=77：23), 1000 ㎏ methyl alcohol and the isobutyl of 0.3 ㎏ azos two
Nitrile, stirs and is warming up to 66 DEG C, and copolymerization is after 5 hours, is cooled to 30 DEG C, then to adding 175 ㎏ 15%wt in reactor A
Sodium hydroxide solution, after carrying out alcoholysis 5 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carry out separation of solid and liquid, then use
Proper amount of methanol washing solid phase is filtered afterwards for several times, dries its filter cake, and filter cake is obtained ionic polyvinyl resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 10.8% at 95 DEG C, after then cooling to 30 DEG C, 58 ㎏ aldehyde is added under agitation
Class compound and 10 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product
Obtained polyvinyl butyral resin number-average molecular weight 160460, ionic groups molar fraction is 26.2%.
Embodiment 7：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 450 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：PAA=93：7), 1000 ㎏ methyl alcohol and 0.15 ㎏ azodiisobutyronitriles,
61 DEG C are stirred and be warming up to, copolymerization is after 5 hours, be cooled to 30 DEG C, then to adding 170 ㎏ 15%wt's in reactor A
Sodium hydroxide solution, after carrying out alcoholysis 4 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carries out separation of solid and liquid, then with suitable
Amount methyl alcohol washing solid phase is filtered afterwards for several times, dries its filter cake, and filter cake is obtained ionic polyvinyl resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 14.2% at 95 DEG C, after then cooling to 25 DEG C, 50 ㎏ aldehyde is added under agitation
Class compound and 17 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 160335, ionic groups molar fraction is 3.7%.
Embodiment 8：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 340 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：SSS：Methacrylic sulfonic acid=89：5：6), 1000 ㎏ methyl alcohol and
0.1 ㎏ azodiisobutyronitriles, stir and are warming up to 56 DEG C, and copolymerization is cooled to 30 DEG C after 4.5 hours, then to reactor A
The sodium hydroxide solution of 176 ㎏ 15%wt of middle addition, after carrying out alcoholysis 4 hours, with appropriate acetic acid neutralization reaction medium to neutrality,
Separation of solid and liquid is carried out, then solid phase is washed with proper amount of methanol to filter afterwards for several times, dry its filter cake, filter cake is the poly- second of obtained ionic
Enol resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 11.2% at 95 DEG C, after then cooling to 18 DEG C, 59 ㎏ aldehyde is added under agitation
Class compound and 16 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 160462, ionic groups molar fraction is 7.5%.
Embodiment 9：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 430 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Acrylic acid：ALS=92：4：4), 1000 ㎏ methyl alcohol and 0.4 ㎏ idols
Nitrogen bis-isobutyronitrile, stirs and is warming up to 64 DEG C, and copolymerization is after 4 hours, is cooled to 30 DEG C, then to adding 183 in reactor A
The sodium hydroxide solution of ㎏ 15%wt, after carrying out alcoholysis 5 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carries out solid-liquid
Separate, then solid phase is washed with proper amount of methanol and filter afterwards for several times, dry its filter cake, filter cake is obtained ionic polyvinyl resin
Pellet；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 9.3% at 95 DEG C, after then cooling to 22 DEG C, 66 ㎏ aldehyde is added under agitation
Class compound and 13 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 78100, ionic groups molar fraction is 3.7%.
Embodiment 10：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 400 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Acrylic acid：Methacrylic acid=90：3：7), 1000 ㎏ methyl alcohol and 0.1~0.5
㎏ azodiisobutyronitriles, stir and are warming up to 67 DEG C, and copolymerization is cooled to 30 DEG C after 4.5 hours, then in reactor A
The sodium hydroxide solution of 187 ㎏ 15%wt is added, after carrying out alcoholysis 4.5 hours, with appropriate acetic acid neutralization reaction medium to neutrality,
Separation of solid and liquid is carried out, then solid phase is washed with proper amount of methanol to filter afterwards for several times, dry its filter cake, filter cake is the poly- second of obtained ionic
Enol resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 9.6% at 95 DEG C, after then cooling to 20 DEG C, 64 ㎏ aldehyde is added under agitation
Class compound and 12 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 77560, ionic groups molar fraction is 7.8%.
Embodiment 11：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 330 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Sodium vinyl sulfonate：ALS=80：12：8), 1000 ㎏ methyl alcohol and
0.45 ㎏ azodiisobutyronitriles, stir and are warming up to 60 DEG C, and copolymerization is cooled to 30 DEG C after 4.5 hours, then to reactor
The sodium hydroxide solution of 195 ㎏ 15%wt is added in A, after carrying out alcoholysis 4 hours, with appropriate acetic acid neutralization reaction medium into
Property, separation of solid and liquid is carried out, then solid phase is washed with proper amount of methanol to filter afterwards for several times, its filter cake is dried, filter cake is obtained ionic
Polyvinyl alcohol resin pellet；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 13.9% at 95 DEG C, after then cooling to 28 DEG C, 61 ㎏ aldehyde is added under agitation
Class compound and 10 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 5 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 13712, ionic groups molar fraction is 18.1%.
Embodiment 12：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 380 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：PAA：Methacrylic sulfonic acid=72：16：12), 1000 ㎏ methyl alcohol and 0.3
㎏ azodiisobutyronitriles, stir and are warming up to 55 DEG C, and copolymerization is cooled to 30 DEG C, then add in reactor A after 4 hours
Enter the sodium hydroxide solution of 174 ㎏ 15%wt, after carrying out alcoholysis 5 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carry out
Separation of solid and liquid, then solid phase is washed with proper amount of methanol filter afterwards for several times, its filter cake is dried, filter cake is obtained ionic polyvinyl
Resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 13.6% at 95 DEG C, after then cooling to 29 DEG C, 60 ㎏ aldehyde is added under agitation
Class compound and 13 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 13750, ionic groups molar fraction is 25.6%.
Embodiment 13：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 460 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Sodium methacrylate：ALS：Methacrylic sulfonic acid=88：5：3：
4), 1000 ㎏ methyl alcohol and 0.2 ㎏ azodiisobutyronitriles, stir and are warming up to 70 DEG C, and copolymerization is cooled to 30 after 5 hours
DEG C, then to the sodium hydroxide solution of 191 ㎏ 15%wt is added in reactor A, after carrying out alcoholysis 4.5 hours, with appropriate acetic acid
With reaction medium to neutrality, separation of solid and liquid is carried out, then solid phase is washed with proper amount of methanol to filter afterwards for several times, dry its filter cake, filter cake
I.e. obtained ionic polyvinyl resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 8.0% at 95 DEG C, after then cooling to 20 DEG C, 55 ㎏ aldehyde is added under agitation
Class compound and 15 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 17269, ionic groups molar fraction is 10.0%.
Embodiment 14：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 410 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Acrylic acid：Methacrylic acid：Vinyl sulfonic acid：SSS：Pi-allyl
Sulfonic acid：Methacrylic sulfonic acid=79：13：8), 1000 ㎏ methyl alcohol and 0.25 ㎏ azodiisobutyronitriles, stir and are warming up to 65 DEG C,
After copolymerization 4 hours, 30 DEG C are cooled to, then to the sodium hydroxide solution of 175 ㎏ 15%wt is added in reactor A, carry out
After alcoholysis 4 hours, with appropriate acetic acid neutralization reaction medium to neutrality, separation of solid and liquid is carried out, then solid phase number is washed with proper amount of methanol
Filtering, dries its filter cake after secondary, and filter cake is obtained ionic polyvinyl resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 9.4% at 95 DEG C, after then cooling to 18 DEG C, 62 ㎏ aldehyde is added under agitation
Class compound and 17 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 7 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 17330, ionic groups molar fraction is 18.5%.
Embodiment 15：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 360 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：SSS=75：25), 1000 ㎏ methyl alcohol and the isobutyl of 0.1 ㎏ azos two
Nitrile, stirs and is warming up to 59 DEG C, and copolymerization is after 5 hours, is cooled to 30 DEG C, then to adding 178 ㎏ 15%wt in reactor A
Sodium hydroxide solution, after carrying out alcoholysis 4.5 hours, with appropriate acetic acid neutralization reaction medium to neutrality, carry out separation of solid and liquid, then
Solid phase is washed with proper amount of methanol to filter afterwards for several times, its filter cake is dried, and filter cake is obtained ionic polyvinyl resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 6.1% at 95 DEG C, after then cooling to 21 DEG C, 64 ㎏ aldehyde is added under agitation
Class compound and 14 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 5 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 18060, ionic groups molar fraction is 21.3%.
Embodiment 16：
Synthesis ionic polyvinyl resin：First with air in nitrogen displacement reactor A, to adding 300 ㎏ in reactor A
(mol ratio is mix monomer：Vinylacetate：Styrene sulfonic acid：ALS=70：15：15), 1000 ㎏ methyl alcohol and
0.5 ㎏ azodiisobutyronitriles, stir and are warming up to 68 DEG C, and copolymerization is cooled to 30 DEG C after 4.5 hours, then to reactor A
The sodium hydroxide solution of 170 ㎏ 15%wt of middle addition, after carrying out alcoholysis 5 hours, with appropriate acetic acid neutralization reaction medium to neutrality,
Separation of solid and liquid is carried out, then solid phase is washed with proper amount of methanol to filter afterwards for several times, dry its filter cake, filter cake is the poly- second of obtained ionic
Enol resin granular material；
Synthesis ionic polyvinyl butyral (IPVB)：100 ㎏ ionic polyvinyls resins are added into reactor B
In, dissolving is made into the aqueous solution of mass fraction 6.3% at 95 DEG C, after then cooling to 21 DEG C, 67 ㎏ aldehyde is added under agitation
Class compound and 15 ㎏ hydrochloric acid (hydrochloric acid consumption is calculated with HCl) are reacted, and after being warming up to 55 DEG C of reactions 6 hours, are cooled to 35
DEG C filtering, filter cake 500 ㎏ water every time is dried, i.e., obtained ionic polyvinyl butyral resin after washing 6 times
Finished product.
Obtained polyvinyl butyral resin number-average molecular weight 18130, ionic groups molar fraction is 18.7%.
In order to better illustrate the features of the present invention, by differential thermal analysis (DSC) and dynamic mechanical analysis (DMA) to being closed
Into ionic PVB resin carried out the test of glass transition temperature and storage modulus.
Glass transition temperature tester model NETZSCH DCS214, under nitrogen protection with the liter of 20K/min
Warm speed is tested.
Laminated glass manufacturing process：Synthesized ionic PVB resin is with tetraethylene glycol bis-enanthate (4G7) in mass ratio
72: 28 proportioning passes through extruder casting film-forming.90 DEG C of section temperature that feeds intake of extruder, melt zone is 170 DEG C, and die head temperature is
140 DEG C, resulting PVB film thickness is 0.76 ± 0.02mm.Using the storage of TA Q800 Dynamic Mechanical Analyzer test films
Energy modulus G ＇, test temperature is 25 DEG C, 40 DEG C, 60 DEG C, 160 DEG C.
In order to more preferably illustrate the feature of ionic PVB of the present invention, will be with the common PVB of molecular weight grades and ionic PVB
Contrasted, plexiglas transition temperature and film storage modulus G ＇ data are listed in the table below.
Table 1：With the common PVB of molecular weight grades and ionic PVB performance comparison tables：
Embodiment 17：
A kind of preparation method of ionic polyvinyl butyral (abbreviation IPVB) resin, step is：
A, synthesis ionic polyvinyl resin：The air in reactor A first is removed with nitrogen displacement, then to reactor A
300 mass parts mix monomers of middle addition, 1000 mass parts Methanols and 0.1 mass parts azodiisobutyronitrile, stir and are warming up to 55
DEG C, copolymerization is after 4 hours, is cooled to 30 DEG C, then to adding the 170 mass parts mass percent concentrations to be in reactor A
15% sodium hydrate aqueous solution, after carrying out alcoholysis 5 hours, with (appropriate) acetic acid neutralization reaction medium to neutrality, filtering (is carried out
Separation of solid and liquid), solids is washed 3 times with (appropriate) methyl alcohol, then by solids (i.e. filter cake) dry after, as obtained ionic
Polyvinyl alcohol resin (pellet)；
The mix monomer is the mixture of vinylacetate and ionic comonomer；
The ionic comonomer is the ionic acid compounds containing unsaturated double-bond and the ion containing unsaturated double-bond
One or more mixture in type salt compounds；
B, synthesis ionic polyvinyl butyral：100 mass parts ionic polyvinyl resins are added into reactor B
In, dissolved at 95 DEG C and be configured to the ionic polyvinyl resin aqueous solution that mass percent concentration is 6%, then lower the temperature
To after 15 DEG C, add under agitation 50 mass parts aldehyde compounds and 6 mass parts hydrochloric acid (the mass parts consumption of hydrochloric acid with HCl i.e.
The mass parts of hydrogen chloride are calculated) mixed, after being warming up to 55 DEG C of reactions 5 hours, 35 DEG C of filterings are cooled to, by solids (i.e.
Filter cake) use 500 mass parts water washing 4 times every time, then by solids (i.e. filter cake) dry after, as obtained ionic polyethylene
Polyvinyl butyral resin (finished product)；
The aldehyde compound be butyraldehyde with C5~C8 aliphatic aldehydes compound, C5~C8 aromatic aldehyde compounds in extremely
A kind of the constituted mixture of few mixing.
Embodiment 18：
A kind of preparation method of ionic polyvinyl butyral (abbreviation IPVB) resin, step is：
A, synthesis ionic polyvinyl resin：The air in reactor A first is removed with nitrogen displacement, then to reactor A
500 mass parts mix monomers of middle addition, 1000 mass parts Methanols and 0.5 mass parts azodiisobutyronitrile, stir and are warming up to 70
DEG C, copolymerization is after 4 hours, is cooled to 30 DEG C, then to adding the 195 mass parts mass percent concentrations to be in reactor A
15% sodium hydrate aqueous solution, after carrying out alcoholysis 5 hours, with (appropriate) acetic acid neutralization reaction medium to neutrality, filtering (is carried out
Separation of solid and liquid), solids is washed 6 times with (appropriate) methyl alcohol, then by solids (i.e. filter cake) dry after, as obtained ionic
Polyvinyl alcohol resin (pellet)；
The mix monomer is the mixture of vinylacetate and ionic comonomer；
The ionic comonomer is the ionic acid compounds containing unsaturated double-bond and the ion containing unsaturated double-bond
One or more mixture in type salt compounds；
B, synthesis ionic polyvinyl butyral：100 mass parts ionic polyvinyl resins are added into reactor B
In, dissolved at 95 DEG C and be configured to the ionic polyvinyl resin aqueous solution that mass percent concentration is 15%, then drop
After warm to 32 DEG C, 67 mass parts aldehyde compounds and 20 mass parts hydrochloric acid are added under agitation, and (the mass parts consumption of hydrochloric acid is with HCl
I.e. hydrogen chloride mass parts calculate) mixed, be warming up to 55 DEG C reaction 7 hours after, 35 DEG C of filterings are cooled to, by solids
(i.e. filter cake) use 500 mass parts water washing 6 times every time, then by solids (i.e. filter cake) dry after, as obtained ionic gather
Vinyl butyral resin (finished product)；
The aldehyde compound be butyraldehyde with C5~C8 aliphatic aldehydes compound, C5~C8 aromatic aldehyde compounds in extremely
A kind of the constituted mixture of few mixing.
Embodiment 19：
A kind of preparation method of ionic polyvinyl butyral (abbreviation IPVB) resin, step is：
A, synthesis ionic polyvinyl resin：The air in reactor A first is removed with nitrogen displacement, then to reactor A
400 mass parts mix monomers of middle addition, 1000 mass parts Methanols and 0.3 mass parts azodiisobutyronitrile, stir and are warming up to 63
DEG C, copolymerization is after 4.5 hours, is cooled to 30 DEG C, then to adding the 182 mass parts mass percent concentrations to be in reactor A
15% sodium hydrate aqueous solution, after carrying out alcoholysis 4.5 hours, with (appropriate) acetic acid neutralization reaction medium to neutrality, filtering (is entered
Row separation of solid and liquid), solids is washed 5 times with (appropriate) methyl alcohol, then by solids (i.e. filter cake) dry after, as obtained ion
Type polyvinyl alcohol resin (pellet)；
The mix monomer is the mixture of vinylacetate and ionic comonomer；
The ionic comonomer is the ionic acid compounds containing unsaturated double-bond and the ion containing unsaturated double-bond
One or more mixture in type salt compounds；
B, synthesis ionic polyvinyl butyral：100 mass parts ionic polyvinyl resins are added into reactor B
In, dissolved at 95 DEG C and be configured to the ionic polyvinyl resin aqueous solution that mass percent concentration is 10%, then drop
After warm to 23 DEG C, 58 mass parts aldehyde compounds and 13 mass parts hydrochloric acid are added under agitation, and (the mass parts consumption of hydrochloric acid is with HCl
I.e. hydrogen chloride mass parts calculate) mixed, be warming up to 55 DEG C reaction 6 hours after, 35 DEG C of filterings are cooled to, by solids
(i.e. filter cake) use 500 mass parts water washing 5 times every time, then by solids (i.e. filter cake) dry after, as obtained ionic gather
Vinyl butyral resin (finished product)；
The aldehyde compound be butyraldehyde with C5~C8 aliphatic aldehydes compound, C5~C8 aromatic aldehyde compounds in extremely
A kind of the constituted mixture of few mixing.
Embodiment 20~26：
A kind of preparation method of ionic polyvinyl butyral (abbreviation IPVB) resin, step is：
A, synthesis ionic polyvinyl resin：The air in reactor A first is removed with nitrogen displacement, then to reactor A
300~500 mass parts mix monomers of middle addition, 1000 mass parts Methanols and 0.1~0.5 mass parts azodiisobutyronitrile, stirring
And it is any in being warming up to 55~70 DEG C, in copolymerization 4~5 after any hour, 30 DEG C are cooled to, then add in reactor A
Enter the sodium hydrate aqueous solution that 170~195 mass parts mass percent concentrations are 15%, carry out any hour in alcoholysis 4~5
Afterwards, with (appropriate) acetic acid neutralization reaction medium to neutrality, filter (carrying out separation of solid and liquid), solids washs 3 with (appropriate) methyl alcohol
It is any in~6 times, then by solids (i.e. filter cake) dry after, as obtained ionic polyvinyl resin (pellet)；
The specific mass parts consumption (unit of mass parts of each component in embodiment 22-26：Gram) see the table below：
The mix monomer is the mixture of vinylacetate and ionic comonomer；
The ionic comonomer is the ionic acid compounds containing unsaturated double-bond and the ion containing unsaturated double-bond
One or more mixture in type salt compounds；
B, synthesis ionic polyvinyl butyral：100 mass parts ionic polyvinyl resins are added into reactor B
In, dissolve at 95 DEG C and be configured to the ionic polyvinyl resin of any concentration during mass percent concentration is 6~15%
The aqueous solution, it is any in then cooling to 15~32 DEG C after, under agitation add 50~67 mass parts aldehyde compounds and 6~20 matter
Amount part hydrochloric acid (the mass parts consumption of hydrochloric acid is calculated with the mass parts that HCl is hydrogen chloride) is mixed, be warming up to 55 DEG C of reactions 5~
In 7 after any hour, 35 DEG C of filterings are cooled to, by solids (i.e. filter cake) with appointing in 500 mass parts water washing every time 4~6 times
One, then by solids (i.e. filter cake) dry after, as obtained ionic polyvinyl butyral resin (finished product)；
The specific mass parts consumption (unit of mass parts of each component in embodiment 22-26：Gram) see the table below：
The aldehyde compound be butyraldehyde with C5~C8 aliphatic aldehydes compound, C5~C8 aromatic aldehyde compounds in extremely
A kind of the constituted mixture of few mixing.
Embodiment 27：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer is vinyl acetate described in step a
The mixture of ester and ionic comonomer, wherein：The mole percentage of vinylacetate is the mole of 70%, ionic comonomer
Percentage is 30%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 28：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer is vinyl acetate described in step a
The mixture of ester and ionic comonomer, wherein：The mole percentage of vinylacetate is the mole of 98%, ionic comonomer
Percentage is 2%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 29：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer is vinyl acetate described in step a
The mixture of ester and ionic comonomer, wherein：The mole percentage of vinylacetate is the mole of 84%, ionic comonomer
Percentage is 16%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 30：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer is vinyl acetate described in step a
The mixture of ester and ionic comonomer, wherein：The mole percentage of vinylacetate is the mole of 90%, ionic comonomer
Percentage is 10%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 31：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer is vinyl acetate described in step a
The mixture of ester and ionic comonomer, wherein：The mole percentage of vinylacetate is the mole of 80%, ionic comonomer
Percentage is 20%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 32：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer described in step a is vinyl acetate
The mixture of ester and ionic comonomer, wherein：The mole hundred of the mole percentage 85%, ionic comonomer of vinylacetate
Divide and compare 15%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 33：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer described in step a is vinyl acetate
The mixture of ester and ionic comonomer, wherein：The mole hundred of the mole percentage 95%, ionic comonomer of vinylacetate
Divide and compare 5%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 34：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer described in step a is vinyl acetate
The mixture of ester and ionic comonomer, wherein：The mole hundred of the mole percentage 92%, ionic comonomer of vinylacetate
Divide and compare 8%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 35：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer described in step a is vinyl acetate
The mixture of ester and ionic comonomer, wherein：The mole hundred of the mole percentage 87%, ionic comonomer of vinylacetate
Divide and compare 13%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 36：
A kind of preparation method of ionic polyvinyl butyral resin, mix monomer described in step a is vinyl acetate
The mixture of ester and ionic comonomer, wherein：The mole hundred of the mole percentage 91%, ionic comonomer of vinylacetate
Divide and compare 9%.It is any in the other the same as in Example 1 7~26, omit.
Embodiment 37：
A kind of preparation method of ionic polyvinyl butyral resin, aldehyde compound described in step b can be matter
Amount percentage is 100% butyraldehyde.It is any in the other the same as in Example 1 7~36, omit.
Embodiment 38：
A kind of preparation method of ionic polyvinyl butyral resin, aldehyde compound described in step b can be matter
In amount percentage is 85% butyraldehyde and mass percent is 15% valeral, hexanal, enanthaldehyde, octanal, benzaldehyde, phenylacetaldehyde
The constituted mixture of any one or more mixing.It is any in the other the same as in Example 1 7~36, omit.
Embodiment 39：
A kind of preparation method of ionic polyvinyl butyral resin, aldehyde compound described in step b can be matter
In amount percentage is 93% butyraldehyde and mass percent is 7% valeral, hexanal, enanthaldehyde, octanal, benzaldehyde, phenylacetaldehyde
The constituted mixture of any one or more mixing.It is any in the other the same as in Example 1 7~36, omit.
Embodiment 40：
A kind of preparation method of ionic polyvinyl butyral resin, aldehyde compound described in step b can be matter
In amount percentage is 87% butyraldehyde and mass percent is 13% valeral, hexanal, enanthaldehyde, octanal, benzaldehyde, phenylacetaldehyde
The constituted mixture of any one or more mixing.It is any in the other the same as in Example 1 7~36, omit.
Embodiment 41：
A kind of preparation method of ionic polyvinyl butyral resin, aldehyde compound described in step b can be matter
In amount percentage is 89% butyraldehyde and mass percent is 11% valeral, hexanal, enanthaldehyde, octanal, benzaldehyde, phenylacetaldehyde
The constituted mixture of any one or more mixing.It is any in the other the same as in Example 1 7~36, omit.
Embodiment 42：
A kind of preparation method of ionic polyvinyl butyral resin, aldehyde compound described in step b can be matter
In amount percentage is 95% butyraldehyde and mass percent is 5% valeral, hexanal, enanthaldehyde, octanal, benzaldehyde, phenylacetaldehyde
The constituted mixture of any one or more mixing.It is any in the other the same as in Example 1 7~36, omit.
Embodiment 43：
A kind of preparation method of ionic polyvinyl butyral resin, aldehyde compound described in step b can be matter
In amount percentage is 98% butyraldehyde and mass percent is 2% valeral, hexanal, enanthaldehyde, octanal, benzaldehyde, phenylacetaldehyde
The constituted mixture of any one or more mixing.It is any in the other the same as in Example 1 7~36, omit.
In above-described embodiment 17~43：Ionic comonomer described in step a can be, but not limited to be acrylic acid, metering system
One kind in the salt of acid, vinyl sulfonic acid, styrene sulfonic acid, allyl sulphonic acid, methacrylic sulfonic acid and aforesaid compound or
Or two or more mixtures.
In above-described embodiment 17~43：Contain remnants in the structure of obtained ionic polyvinyl resin described in step a
Acetate, three kinds of groups of ionic groups and vinyl alcohol, wherein：The mole percentage of acetate is 0.05%~0.5%
In the range of, the mole percentage of ionic groups in the range of 2%~25%, remaining (i.e. surplus) be vinyl alcohol.
In above-described embodiment 17~43：Obtained ionic polyvinyl butyral (abbreviation IPVB) described in step b point
Minor structure is made up of acetal radical, vinyl alcohol, ionic groups and acetate, and the mole percentage of wherein ionic groups contains
Amount is in the range of 2%~29%.
In above-described embodiment 17~43：The obtained ionic polyvinyl butyral (abbreviation IPVB) described in step b
Mean molecule quantity in the range of 60000~180000, correlation performance parameters scope is：65~81 DEG C of glass transition temperature,
Storage modulus (at 25 DEG C) 2.36 × 106~6.98 × 106G ＇/Pa, storage modulus (at 40 DEG C) 3.57 × 105~7.33 ×
105G ＇/Pa, storage modulus (at 60 DEG C) 4.45 × 105~7.46 × 105G ＇/Pa, storage modulus (at 160 DEG C) 3.29 × 104
~7.10 × 104G ＇/Pa.
In above-described embodiment：It is especially not dated in the percentage for being used, be quality (weight) percentage or
Well known to a person skilled in the art percentage；In the ratio for being used, do not indicate especially, be quality (weight) ratio；
The weight portion can be gram or kilogram.
In above-described embodiment：Technological parameter (temperature, time, concentration etc.) and each component numerical quantity in each step etc. are
Scope, any point is applicable.
Compared with technology, the raw material are the technology contents being not specifically delineated in present invention and above-described embodiment
Commercially available prod.
The invention is not restricted to above-described embodiment, can implement and with the good result described in present invention.
Claims (9)
1. a kind of preparation method of ionic polyvinyl butyral resin, it is characterized in that step is：
A, synthesis ionic polyvinyl resin：The air in reactor A first is removed with nitrogen displacement, then is added in reactor A
Enter 300~500 mass parts mix monomers, 1000 mass parts Methanols and 0.1~0.5 mass parts azodiisobutyronitrile, stir and rise
To 55~70 DEG C, copolymerization is cooled to 30 DEG C to temperature after 4~5 hours, then to 170~195 mass parts of addition in reactor A
Mass percent concentration is 15% sodium hydrate aqueous solution, after carrying out alcoholysis 4~5 hours, with acetic acid neutralization reaction medium into
Property, filtering, solids washs 3~6 times with methyl alcohol, then after solids is dried, as obtained ionic polyvinyl resin；
The mix monomer is the mixture of vinylacetate and ionic comonomer；
The ionic comonomer is the ionic acid compounds containing unsaturated double-bond and the ionic salt containing unsaturated double-bond
One or more mixture in class compound；
B, synthesis ionic polyvinyl butyral：By 100 mass parts ionic polyvinyl resins add reactor B in,
The ionic polyvinyl resin aqueous solution that mass percent concentration is 6~15% is dissolved and be configured at 95 DEG C, is then cooled to
After 15~32 DEG C, add 50~67 mass parts aldehyde compounds and 6~20 mass parts hydrochloric acid to be mixed under agitation, be warming up to
After 55 DEG C are reacted 5~7 hours, 35 DEG C of filterings are cooled to, by solids 500 mass parts water washing 4~6 times every time, then will be solid
After body thing is dried, as obtained ionic polyvinyl butyral resin；
The aldehyde compound be butyraldehyde with C5~C8 aliphatic aldehydes compound, C5~C8 aromatic aldehyde compounds at least one
Plant the constituted mixture of mixing.
2. as described in claim 1 ionic polyvinyl butyral resin preparation method, it is characterized in that：Described in step a
Mix monomer is the mixture of vinylacetate and ionic comonomer, wherein：The mole percentage of vinylacetate be 70%~
98%th, the mole percentage of ionic comonomer is 2%~30%.
3. as described in claim 1 ionic polyvinyl butyral resin preparation method, it is characterized in that：Described in step a
Mix monomer is the mixture of vinylacetate and ionic comonomer, wherein：The mole percentage 85% of vinylacetate~
95%th, the mole percentage 5%~15% of ionic comonomer.
4. as described in claim 1,2 or 3 ionic polyvinyl butyral resin preparation method, it is characterized in that：In step a
The ionic comonomer is acrylic acid, methacrylic acid, vinyl sulfonic acid, styrene sulfonic acid, allyl sulphonic acid, metering system sulphur
One kind or or two or more mixture in the salt of acid and aforesaid compound.
5. as described in claim 1,2 or 3 ionic polyvinyl butyral resin preparation method, it is characterized in that：In step b
The aldehyde compound is the butyraldehyde that mass percent is 85%~100% and valeral, hexanal, heptan that mass percent is 0~15%
Any one or more in aldehyde, octanal, benzaldehyde, phenylacetaldehyde mix constituted mixture.
6. as described in claim 4 ionic polyvinyl butyral resin preparation method, it is characterized in that：Described in step b
Aldehyde compound be butyraldehyde that mass percent is 85%~100% with the valeral, hexanal, enanthaldehyde that mass percent is 0~15%,
Any one or more in octanal, benzaldehyde, phenylacetaldehyde mix constituted mixture.
7. as described in claim 1 ionic polyvinyl butyral resin preparation method, it is characterized in that：Made described in step a
Containing remaining acetate, three kinds of groups of ionic groups and vinyl alcohol in the structure of the ionic polyvinyl resin for obtaining, its
In：The mole percentage of acetate be 0.05%~0.5%, ionic groups mole percentage for 2%~25%, remaining be
Vinyl alcohol.
8. as described in claim 1 ionic polyvinyl butyral resin preparation method, it is characterized in that：Made described in step b
The molecular structure of the ionic polyvinyl butyral for obtaining is made up of acetal radical, vinyl alcohol, ionic groups and acetate, its
The mole degree of ionic group is 2%~29%.
9. as described in claim 1 ionic polyvinyl butyral resin preparation method, it is characterized in that：Made described in step b
The ionic polyvinyl butyral for obtaining（Abbreviation IPVB）Mean molecule quantity be 60000~180000, glass transition
65~81 DEG C of temperature, storage modulus（At 25 DEG C）2.36×106~6.98 × 106G＇/ Pa, storage modulus（At 40 DEG C）3.57×
105~7.33 × 105G＇/ Pa, storage modulus（At 60 DEG C）4.45×105~7.46 × 105G＇/ Pa, storage modulus（At 160 DEG C）
3.29×104~7.10 × 104G＇/Pa。
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|---|---|---|---|---|
| CN1261605A (en) * | 1998-12-09 | 2000-08-02 | 可乐丽股份有限公司 | Vinyl alcohol polymer and its composition |
| CN1675259A (en) * | 2002-09-12 | 2005-09-28 | 瓦克聚合系统两合公司 | Method for producing polyvinylacetals |
| CN102746462A (en) * | 2012-07-19 | 2012-10-24 | 安徽皖维高新材料股份有限公司 | Method for preparing water-soluble polyvinyl acetate (PVA) resin through vinyl acetate-acrylic acid copolymerization |
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2016
- 2016-12-21 CN CN201611192065.6A patent/CN106832067A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1261605A (en) * | 1998-12-09 | 2000-08-02 | 可乐丽股份有限公司 | Vinyl alcohol polymer and its composition |
| CN1675259A (en) * | 2002-09-12 | 2005-09-28 | 瓦克聚合系统两合公司 | Method for producing polyvinylacetals |
| CN102746462A (en) * | 2012-07-19 | 2012-10-24 | 安徽皖维高新材料股份有限公司 | Method for preparing water-soluble polyvinyl acetate (PVA) resin through vinyl acetate-acrylic acid copolymerization |
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