CN103333279A - Production method of novel zwitterionic polyvinyl butyral resin - Google Patents
Production method of novel zwitterionic polyvinyl butyral resin Download PDFInfo
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- CN103333279A CN103333279A CN2013102898611A CN201310289861A CN103333279A CN 103333279 A CN103333279 A CN 103333279A CN 2013102898611 A CN2013102898611 A CN 2013102898611A CN 201310289861 A CN201310289861 A CN 201310289861A CN 103333279 A CN103333279 A CN 103333279A
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- acrylamide
- polyvinyl butyral
- butyral resin
- production method
- dihydroxyalkyl
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- 229920005989 resin Polymers 0.000 title claims abstract description 39
- 239000011347 resin Substances 0.000 title claims abstract description 39
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006359 acetalization reaction Methods 0.000 claims description 5
- LPNSCOVIJFIXTJ-UHFFFAOYSA-N 2-methylidenebutanamide Chemical compound CCC(=C)C(N)=O LPNSCOVIJFIXTJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- CFMVCKMWMQJGJQ-UHFFFAOYSA-N N-(3,3-dihydroxypropyl)prop-2-enamide Chemical compound C(C=C)(=O)NCCC(O)O CFMVCKMWMQJGJQ-UHFFFAOYSA-N 0.000 claims description 2
- HZHRYYYIOGLPCB-UHFFFAOYSA-N n,n-bis(hydroxymethyl)prop-2-enamide Chemical group OCN(CO)C(=O)C=C HZHRYYYIOGLPCB-UHFFFAOYSA-N 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 abstract description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003373 anti-fouling effect Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 239000011354 acetal resin Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical group O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CUNSSTRCJPDQFY-UHFFFAOYSA-N n-(dihydroxymethyl)prop-2-enamide Chemical compound OC(O)NC(=O)C=C CUNSSTRCJPDQFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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Abstract
The invention discloses a production method of a novel zwitterionic polyvinyl butyral resin. The method comprises the following steps: introducing a zwitterionic group to a high-molecular chain, carrying out acetalation for positioning the zwitterionic group, butyral, vinyl alcohol and a less amount of a vinyl acetate constitutional unit in a same high-molecular chain, and controlling the synthesis technology conditions to obtain the novel polyvinyl butyral resin having a bonding resistance and an antifouling performance. The zwitterionic group is connected with the vinyl alcohol unit on the high-molecular chain through an alkyl ether bond, so the axial rotation of a C-O-C bond in the side chain along the carbon chain and the flexibility of a film are not influenced, the tensile break strength and the impact strength of the film are good, and the transparency, haze and the like of the film can satisfy application requirements.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of production method of new type amphoteric ionic polyvinyl butyral resin.
Background technology
Polyvinyl butyral resin (PVB), be that polyvinyl alcohol resin carries out the functional thermoplastic resin that acetalation generates in acid catalyst effect and butyraldehyde, contain vinyl alcohol, butyral six-ring and vinyl acetate structural unit in the molecular structure, also can be regarded as the multipolymer of vinyl alcohol, vinyl acetate, butyral structure; Change the composition of different structure unit on the resin polymer chain, the performance that just can regulate the PVB resin is to satisfy the requirement in different application field.
Polyvinyl butyral resin (PVB) has good film forming properties, optical property and UV resistant and resistance toheat, and glass, metal etc. is had good viscosifying power, mainly is used as the sandwich material of windshield, building safety glass; The production field that also is used for ceramic decorative pattern, tackiness agent, textile sizing, paper surface coating, solar cell, photovoltaic cell.
Usually the many employings of polyvinyl butyral resin are in the precipitator method of aqueous phase, and perhaps the homogeneous phase method is produced in organic solvent.Because the most of hydroxyl in the polyvinyl alcohol molecular structure is by butyraldehyde acetalsization, the hydrogen bond action between the hydroxyl is weakened, so the degree of crystallinity of polyvinyl butyral resin descends, and second-order transition temperature reduces, and water-solublely also reduces with the increase of degree of acetalization.The polyvinyl acetal resin film of the resin after especially plastifying through softening agent or the certain specification that is processed into, second-order transition temperature is lower, and snappiness is better, has certain tensile break strength and resistance to impact shock.
But because the special structure of polyvinyl butyral resin, the influence of the diaphragm of toner, plasticized granule or processing factors such as meeting Yin Wendu, humidity in transportation, storage and use under given conditions, adhere to, conglomeration, the mutual situation of bonding, influence use and the performance in later stage; Usually adopt and sprinkle between pvb film that inorganic powder is isolated or isolate to alleviate this problem with polyethylene (PE) film, not only increase cost, and effect is also unsatisfactory, also might influence intensity and the Key Performance Indicators such as the transparency, mist degree of mechanical property and optical property, the especially diaphragm of resin or its diaphragm.
For addressing this problem, there is the investigator to adopt the polyvinyl alcohol of certain molecular weight and degree of hydrolysis and adjacent formyl radical Phenylsulfonic acid to carry out acetalation, obtain containing on the macromolecular chain ionic Derlin IPVBS (anionic is designated as A-IPVBS) of Phenylsulfonic acid negatively charged ion; Then with common polyvinyl butyral resin PVB mixing film forming or plasticizing granulation according to a certain percentage; this processing by two kinds of resin physical mixed/compounding process obtains plasticized granule or Derlin diaphragm; owing to itself belong to physical mixed; consistency between polymer etc. causes structure and inhomogeneous; using or storage process takes place by " being separated " between different polymers easily; have a strong impact on its optics and mechanical property, simultaneously the viscosifying power of base material also is subjected to the influence of blending anionic polyvinyl alcohol Derlin IPVBS amount.
Among the USP4968745; the author at first utilizes the polyvinyl alcohol of the certain polymerization degree of tool and degree of hydrolysis and adjacent formyl radical Phenylsulfonic acid to carry out the anionic resin IPVBS (being designated as A-IVBS) that acetalation obtains certain degree of acetalization; then with this resin and polyvinyl alcohol resin mixed dissolution; under acid catalyst, carry out acetalation with butyraldehyde-n again, obtain containing the Derlin IPVB of sulfonic acid anion ionic.But for the solubility property that guarantees IPVBS and and the consistency of polyvinyl alcohol; when carrying out acetalation with adjacent formyl radical Phenylsulfonic acid; the amount of the negatively charged ion Phenylsulfonic acid group of introducing (or the degree of acetalization of acetalation) for the first time is very limited; anti-adhesion effect is also very limited; simultaneously resin or/diaphragm descends to the cohesive force of base material such as glass, metal, transparency descends, mist degree increases.
Aforementioned techniques is introduced in resin complexes and is contained Phenylsulfonic acid type negatively charged ion, make resin or diaphragm can take place because the pollution of polyvalent metal ion in improper storage situation, cause the chemically crosslinked of resin polymer chain, diaphragm hardens, yellowing, transparency descend, and tensile break strength and resistance to impact shock descend.
Summary of the invention
The objective of the invention is to overcome the defective that prior art exists, a kind of production method of new type amphoteric ionic polyvinyl butyral resin is provided, by introducing the zwitter-ion group at the polymer chain, and then carry out acetalation, make zwitter-ion group, butyral ring, vinyl alcohol and a spot of vinyl acetate structural unit all be on the same polymer chain, by the control synthetic technological condition, can obtain having the novel polyethylene acetal resin of anti stick and antifouling property.Because the zwitter-ion group is to link to each other with vinyl alcohol units on the polymer chain by the alkyl ehter bond, side-chain structure C-O-C key can axially rotate along carbochain, the snappiness of film is not affected, and the tensile break strength of its diaphragm, resistance to impact shock etc. are superior; The transparency of diaphragm, mist degree etc. all can satisfy the requirement of using.
Its technical scheme is as follows:
A kind of production method of new type amphoteric ionic polyvinyl butyral resin comprises the steps:
1) polyvinyl alcohol of 100g being mixed with concentration is 5%～15% the aqueous solution, be catalyzer with sodium hydroxide or potassium hydroxide, the pH value of regulation system is 9～11, adds the N of 0.045～0.09mol, N-dihydroxyalkyl acrylamide reacted 3～8 hours down at 50～80 ℃;
2) add and N in system, the sodium chloroacetate of N-dihydroxyalkyl acrylamide equimolar amount reacted 30～60 minutes down for described 50～80 ℃ in step 1);
3) the PVA aqueous solution after the modification and butyraldehyde are carried out aldolization under acidic conditions, the acetalation process of existing water method polyvinyl alcohol and butyraldehyde is all applicable, perhaps add alcoholic solvent, separate out the PVA solid after the modification, filter then, drying, replace existing P VA raw material with it, be applicable to the technological process of all nonaqueous phase method production polyvinyl butyral acetals.The degree of acetalization of the finished product is 65%～85%.
Further preferred, described polyvinyl alcohol concentration 8%, pH value 9 adds 0.06molN, N-dihydroxyalkyl acrylamide, 70 ℃ were reacted 4 hours, added the 0.06m01 sodium chloroacetate again, at 70 ℃ of reaction 40min.
Further preferred, described N, N-dihydroxyalkyl acrylamide is N, N-dihydroxymethyl acrylamide, N, N-dihydroxy ethyl acrylamide, N, a kind of or any two or more combination of N-dihydroxypropyl acrylamide.
Further preferred, alcoholic solvent described in the step 3) is mainly a kind of or any two or more combination of methyl alcohol, ethanol, Virahol.
Beneficial effect of the present invention:
The present invention is by introducing the zwitter-ion group at the polymer chain, and then carry out acetalation, make zwitter-ion group, butyral ring, vinyl alcohol and a spot of vinyl acetate structural unit all be on the same polymer chain, by the control synthetic technological condition, can obtain having the novel polyethylene acetal resin of anti stick and antifouling property.Because the zwitter-ion group is to link to each other with vinyl alcohol units on the polymer chain by the alkyl ehter bond, side-chain structure C-O-C key can along carbochain uranium to rotate, the snappiness of film is not affected, the tensile break strength of its diaphragm, resistance to impact shock etc. are superior; The transparency of diaphragm, mist degree etc. all can satisfy the requirement of using.
Description of drawings
Fig. 1 for the present invention with polyvinyl alcohol (PVA) under alkaline condition with N, N-dihydroxyalkyl acrylamide reaction formula;
The PVA that Fig. 2 will introduce tertiary amine group for the present invention again with reaction such as sodium chloroacetate, introduce the reaction formula of betaine type amphoteric ionic group;
Fig. 3 for the PVA of modification under acidic conditions with the butyraldehyde condensation, obtain having the reaction formula that zwitter-ion is hung the polyvinyl butyral resin of group.
Embodiment
Below in conjunction with the drawings and specific embodiments technical scheme of the present invention is done explanation in further detail.
The present invention passes through the modification of the material polyethylene alcohol of synthetic polyvinyl butyral resin is handled, and introduces the amphoteric ion type group, again through obtaining novel ionic polyvinyl butyral resin with the butyraldehyde condensation.
This reaction principle is as follows:
With reference to Fig. 1, with polyvinyl alcohol (PVA) under alkaline condition with N, N-dihydroxyalkyl acrylamide reaction is introduced a spot of tertiary amine group in the agent structure of PVA.
In this process, the group of introducing can not be too much, should be based on 2～4% of hydroxyl, otherwise can have influence on the transformation efficiency of the acetalation of back.
As shown in Figure 2, with the PVA that introduces tertiary amine group again with reaction such as sodium chloroacetate, introduce the betaine type amphoteric ionic group.
As shown in Figure 3, with the PVA of modification under acidic conditions with the butyraldehyde condensation, obtain having the polyvinyl butyral resin of zwitter-ion group.
Embodiment 1:
100gPVA1799 is added in the 900g distilled water, and stirring and dissolving is configured to 10% the PVA aqueous solution, with the pH value to 9 of NaOH regulation system; Add 0.045molN in system, N-dihydroxymethyl acrylamide was 80 ℃ of stirring reactions 3 hours; In system, add the 0.045mol sodium chloroacetate again, at 80 ℃ of stirring reaction 30min.
System is cooled to 10 ℃, and adding 0.25g Sodium dodecylbenzene sulfonate, 9g concentration are 36% hydrochloric acid, mix; And then slow Dropwise 5 7g butyraldehyde-n, drip time 30min.In the reinforced process, system can slightly heat up, and the polyvinyl butyral resin of meeting adularescent begins to separate out, and the hierarchy of control is at 10 ℃ of reaction 30min; Being warming up to 70 ℃ at 90min then, is 10 with 4.5g sodium hydroxide regulation system pH again, keeps 70 ℃ of reaction 60min again, filter, and with 70 ℃ hot washes 4 times, drying, the amphoteric ion type polyvinyl butyral resin 149g that gets final product novelly.
Embodiment 2:
200gPVA2199 is added in the 3800g distilled water, and stirring and dissolving is configured to 5% the PVA aqueous solution, with the pH value to 9 of KOH regulation system; Add 0.18molN in system, N-dihydroxy ethyl acrylamide was 60 ℃ of stirring reactions 5 hours; In system, add the 0.18mol sodium chloroacetate again, at 60 ℃ of stirring reaction 60min.
System is cooled to 12 ℃, and adding 0.45g MALEIC ANHYDRIDE dioctyl ester sodium sulfonate, 20g concentration are 36% hydrochloric acid, mix; And then slowly drip the 120g butyraldehyde-n, drip time 60min.In the reinforced process, system can slightly heat up, and the polyvinyl butyral resin of meeting adularescent begins to separate out, and the hierarchy of control is at 10～12 ℃ of reaction 60nin; Being warming up to 70 ℃ at 120min then, is 10 with 9.2g sodium hydroxide regulation system pH again, keeps 70 ℃ of reaction 60min again, filter, and with 65 ℃ hot washes 3 times, drying, the amphoteric ion type polyvinyl butyral resin 302 that gets final product novelly.
Embodiment 3:
50gPVA1099 is added in the 284g distilled water, and stirring and dissolving is configured to 15% the PVA aqueous solution, with the pH value to 9 of KOH regulation system; Add 0.03molN in system, N-dihydroxy ethyl acrylamide was 50 ℃ of stirring reactions 6 hours; In system, add the 0.03mol sodium chloroacetate again, at 50 ℃ of stirring reaction 50min.
Add 100g methyl alcohol in the system, system is separated out white solid, filters, drying, obtains the PVA of 51g modification.
PVA after the modification is dissolved in the 459g dimethyl sulfoxide (DMSO), adds 4g sulfuric acid under whipped state, hierarchy of control temperature is 60 ℃ of left and right sides Dropwise 35 g butyraldehyde, and the dropping time is controlled at 40min.After dropwising, be incubated again at 70 ℃ of reaction 100min.Under the state of high-speed stirring, add 82g warm water to system, separate out solid, filter, wash 5 times, drying, the amphoteric ion type PVB resin 83g that gets final product novelly with warm water.
The above; only be the preferable embodiment of the present invention; protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses, and the simple change by technical scheme or equivalence are replaced and all fallen within the scope of protection of the present invention.
Claims (4)
1. the production method of a new type amphoteric ionic polyvinyl butyral resin is characterized in that, comprises the steps:
1) polyvinyl alcohol of 100g being mixed with concentration is 5%～15% the aqueous solution, be catalyzer with sodium hydroxide or potassium hydroxide, the pH value of regulation system is 9～11, adds the N of 0.045～0.09mol, N-dihydroxyalkyl acrylamide reacted 3～8 hours down at 50～80 ℃;
2) add and N in system, the sodium chloroacetate of N-dihydroxyalkyl acrylamide equimolar amount reacted 30～60 minutes down for described 50～80 ℃ in step 1);
3) the PVA aqueous solution after the modification and butyraldehyde are carried out aldolization under acidic conditions, the acetalation process of existing water method polyvinyl alcohol and butyraldehyde is all applicable, perhaps add alcoholic solvent, separate out the PVA solid after the modification, filter then, drying, the degree of acetalization of the finished product is 65%～85%.
2. the production method of new type amphoteric ionic polyvinyl butyral resin according to claim 1, it is characterized in that, described polyvinyl alcohol concentration 8%, pH value 9, add 0.06molN, N-dihydroxyalkyl acrylamide, 70 ℃ were reacted 4 hours, add the 0.06mol sodium chloroacetate again, at 70 ℃ of reaction 40min.
3. the production method of new type amphoteric ionic polyvinyl butyral resin according to claim 1, it is characterized in that, described N, N-dihydroxyalkyl acrylamide is N, N-dihydroxymethyl acrylamide, N, N-dihydroxy ethyl acrylamide, N, a kind of or any two or more combination of N-dihydroxypropyl acrylamide.
4. the production method of new type amphoteric ionic polyvinyl butyral resin according to claim 1 is characterized in that, alcoholic solvent described in the step 3) is mainly a kind of or any two or more combination of methyl alcohol, ethanol, Virahol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4968745A (en) * | 1988-11-07 | 1990-11-06 | Monsanto Company | Method of producing ionomeric polyvinyl butyral |
| CN101445570A (en) * | 2008-12-25 | 2009-06-03 | 天津市职业大学 | Method for synthesizing ionic polyvinyl butyral latex |
| CN102516426A (en) * | 2011-11-28 | 2012-06-27 | 怀集县集美新材料有限公司 | High-elasticity polyvinyl butyral as well as synthetic method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4968745A (en) * | 1988-11-07 | 1990-11-06 | Monsanto Company | Method of producing ionomeric polyvinyl butyral |
| CN101445570A (en) * | 2008-12-25 | 2009-06-03 | 天津市职业大学 | Method for synthesizing ionic polyvinyl butyral latex |
| CN102516426A (en) * | 2011-11-28 | 2012-06-27 | 怀集县集美新材料有限公司 | High-elasticity polyvinyl butyral as well as synthetic method and application thereof |
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