CN104141259B - A kind of environment-friendly type cation phenylpropyl surface sizing agent and preparation method thereof - Google Patents
A kind of environment-friendly type cation phenylpropyl surface sizing agent and preparation method thereof Download PDFInfo
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- CN104141259B CN104141259B CN201410311221.0A CN201410311221A CN104141259B CN 104141259 B CN104141259 B CN 104141259B CN 201410311221 A CN201410311221 A CN 201410311221A CN 104141259 B CN104141259 B CN 104141259B
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Abstract
The invention discloses a kind of environment-friendly type cation phenylpropyl surface sizing agent, comprise the component of following parts by weight: the dispersant of 10～15 parts, the oxidant of 5～8 parts, the initator of 0.05～2 part, the hard monomer of 8～10 parts, the soft monomer of 5～8 parts, the acid of 2～3 parts and the water of 50～80 parts. Meanwhile, the invention also discloses the preparation method of above-mentioned Cypres. The present invention is environment friendly and pollution-free, have good compatibility and stability between raw material, has greatly improved the water-resistance of paper, surface strength after applying glue, can also effectively improve smoothness and the printing performance of paper; Production technology is simple, is convenient to suitability for industrialized production, and production cost is low.
Description
Technical field
The present invention relates to pulp technology for making paper, be specifically related to a kind of environment-friendly type cation phenylpropyl surface sizing agent andPreparation method.
Background technology
Along with the development of paper technology, also more and more higher to the performance requirement of paper. Top sizing has become solutionThe main direction of studying of surface strength of paper, water-resistance, printing adaptability. Synthetic class phenylpropyl surface sizing agent,Mainly with starch and modifier thereof, PVA, PMA etc. But due to starch have abundant raw material, with low cost,Use nontoxic pollution-free and advantage that can chemical modification to be widely used. Wherein cation cassava starch is exactly oneKind of novel starch derivative has good result of use in paper industry, but starch after modification has pointSon amount is large, after applying glue paper resistance to water, surface strength do not reach the requirement of special paper kind and complex manufacturing,Applying glue high in cost of production shortcoming.
Summary of the invention
Goal of the invention: the object of the invention is to for the deficiencies in the prior art, a kind of environment-friendly type cation is providedPhenylpropyl surface sizing agent.
Another object of the present invention is to provide the preparation method of above-mentioned environment-friendly type cation phenylpropyl surface sizing agent.
Technical scheme: in order to reach foregoing invention object, the present invention is specifically achieved like this: a kind of environmental protectionType cation phenylpropyl surface sizing agent, comprises the component of following parts by weight: the dispersant, 5 of 10～15 parts～The oxidant of 8 parts, the initator of 0.05～2 part, 8～10 parts hard monomer, 5～8 parts soft monomer, 2～The water of the acid of 3 parts and 50～80 parts.
Wherein, described Cypres can also comprise the component of following parts by weight: the function list of 0～3 partThe cationic monomer of body and 0～1 part; Described function monomer is mainly rosin, and described cationic monomer is poly-twoMethyl diallyl ammonium chloride or MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
Wherein, above-mentioned dispersant is environment-friendly type cation cassava starch or modified starch.
Wherein, above-mentioned oxidant is ammonium persulfate or hydrogen peroxide.
Wherein, above-mentioned initator is ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
Wherein, above-mentioned hard monomer is styrene.
Wherein, above-mentioned soft monomer is butyl acrylate.
Wherein, above-mentioned acid is glacial acetic acid.
The method of preparing above-mentioned arbitrary environment-friendly type cation phenylpropyl surface sizing agent, comprises the following steps:
(1) for subsequent use after getting soft, hard monomer or soft, hard monomer and function monomer and carrying out fully mixing;
(2) initator and water are made to initiator solution in routine 0.5:4～6 in mass ratio;
(3) after by dispersant, fully mix 10:50～60 in mass ratio with water, add oxidant and50% initiator solution (being the initiator solution of half), is warming up to 80～90 DEG C and carries out insulation reaction0.5～1h；
(4) insulation finishes, and adds acid or acid and cationic monomer, and carries out respectively monomer mixture and anotherOuter 50% initiator solution drips, and 80～90 DEG C of dropping temperatures are controlled time for adding 1～3h;
(5) after reinforced, control 80～90 DEG C of insulation reaction 2～3h of temperature;
(6) be cooled to below 50 DEG C, with 200 order net filtrations, discharging, obtain milky cation phenylpropyl alcohol tableSurface sizing agent.
Wherein, the core part that step 4 is preparation method, under acid condition, adds cationic monomer,When improving product cationic degree, control product viscosity, and then increase product stability and serviceability.
Beneficial effect: compared with conventional art, tool of the present invention has the following advantages:
1, the cation cassava starch adopting is dispersant, has advantages of environment friendly and pollution-free;
2, adopt hydrogen peroxide starch is carried out to oxidizing reduction, modification, can make product have good compatibility withAnd stability;
3, greatly improve the water-resistance of paper, surface strength after applying glue, can also effectively improve the level and smooth of paperDegree and printing performance;
4, production technology is simple, is convenient to suitability for industrialized production, and production cost is low.
Detailed description of the invention
Embodiment 1:
Get the tapioca of 10 parts of parts by weight, the ammonium persulfate of 8 parts, the sodium peroxydisulfate of 1 part, the benzene of 9 partsPoly-two of ethene, the butyl acrylate of 7 parts, the glacial acetic acid of 2 parts, the water of 70 parts, the rosin of 3 parts and 1 partMethyl diallyl ammonium chloride is stand-by; Getting butyl acrylate, styrene and rosin carries out fully mixing rear for subsequent use;By sodium peroxydisulfate and water in mass ratio routine 0.5:5 make sodium persulfate aqueous solution; Tapioca and water are pressed to qualityAfter fully mixing than 10:60, add the sodium persulfate aqueous solution of ammonium persulfate and 50%, be warming up to80～90 DEG C are carried out insulation reaction 0.5～1h; Insulation finishes, and adds glacial acetic acid and poly dimethyl allyl chlorineChange ammonium, and carry out respectively the sodium persulfate aqueous solution dropping of monomer mixture and other 50%, dropping temperature80～90 DEG C, control time for adding 1～3h; After reinforced, 80～90 DEG C of insulation reaction 2 of control temperature～3h; Be cooled to below 50 DEG C, with 200 order net filtrations, discharging, obtain milky cation phenylpropyl alcohol surface and executeJelly.
Embodiment 2:
Get the modified starch of 15 parts of parts by weight, the hydrogen peroxide of 5 parts, the potassium peroxydisulfate of 0.5 part, the benzene of 8 partsEthene, the butyl acrylate of 5 parts, the glacial acetic acid of 3 parts, the water of 80 parts are stand-by; Get butyl acrylate, benzene secondAlkene is for subsequent use after carrying out fully mixing; By potassium peroxydisulfate and water in mass ratio routine 0.5:5 make persulfate aqueous solution;After 10:50 fully mixes in mass ratio with water by modified starch, add the persulfuric acid of hydrogen peroxide and 50%Aqueous solutions of potassium, is warming up to 80～90 DEG C and carries out insulation reaction 0.5～1h; Insulation finishes, and adds glacial acetic acid, andThe persulfate aqueous solution that carries out respectively soft monomer and other 50% drips, 80～90 DEG C of dropping temperatures, controlTime for adding 1～3h processed; After reinforced, control 80～90 DEG C of insulation reaction 2～3h of temperature; Be cooled to 50Below DEG C, with 200 order net filtrations, discharging, obtain milky cation phenylpropyl surface sizing agent.
Embodiment 3:
Get the tapioca of 12 parts of parts by weight, the ammonium persulfate of 6 parts, the sodium peroxydisulfate, 10 parts of 2 partsStyrene, the butyl acrylate of 8 parts, the glacial acetic acid of 2 parts, the water of 70 parts, the rosin of 2 parts and the first of 1 partBase acrylyl oxy-ethyl-trimethyl salmiac is stand-by; Getting butyl acrylate, styrene and rosin fully mixesFor subsequent use afterwards; By sodium peroxydisulfate and water in mass ratio routine 0.5:5 make sodium persulfate aqueous solution; By tapioca withWater after 10:50 fully mixes in mass ratio, adds the sodium persulfate aqueous solution of ammonium persulfate and 50%,Be warming up to 80～90 DEG C and carry out insulation reaction 0.5～1h; Insulation finishes, and adds glacial acetic acid and methacryloxypropylEthyl-trimethyl salmiac, and the sodium persulfate aqueous solution that carries out respectively monomer mixture and other 50% dripsAdd, 80～90 DEG C of dropping temperatures, control time for adding 1～3h; After reinforced, control temperature 80～90DEG C insulation reaction 2～3h; Be cooled to below 50 DEG C, with 200 order net filtrations, discharging, obtain milky sun fromSub-phenylpropyl surface sizing agent.
Embodiment 4:
Get the modified starch of 13 parts of parts by weight, the hydrogen peroxide of 7 parts, the ammonium persulfate, 9 parts of 0.05 partStyrene, the butyl acrylate of 6 parts, the glacial acetic acid of 3 parts, the water of 79 parts, the rosin of 1 part and 1 part poly-Dimethyl diallyl ammonium chloride is stand-by; Getting butyl acrylate, styrene and rosin carries out fully mixing rear for subsequent use;By ammonium persulfate and water in mass ratio routine 0.5:6 make ammonium persulfate aqueous solution; Modified starch and water are pressed to qualityAfter fully mixing than 10:60, add the ammonium persulfate aqueous solution of hydrogen peroxide and 50%, be warming up to 80～90 DEG C are carried out insulation reaction 0.5～1h; Insulation finishes, and adds glacial acetic acid and PDDA,And carry out respectively monomer mixture and other 50% ammonium persulfate aqueous solution drip, dropping temperature 80～90DEG C, control time for adding 1～3h; After reinforced, control 80～90 DEG C of insulation reaction 2～3h of temperature; FallTemperature, to below 50 DEG C, with 200 order net filtrations, discharging, obtains milky cation phenylpropyl surface sizing agent.
Embodiment 5:
Get the modified starch of 11 parts of parts by weight, the ammonium persulfate of 8 parts, the sodium peroxydisulfate, 10 parts of 1 partStyrene, the butyl acrylate of 6 parts, the glacial acetic acid of 2 parts, the water of 65 parts are stand-by; Get butyl acrylate, benzeneEthene is for subsequent use after carrying out fully mixing; By sodium peroxydisulfate and water in mass ratio routine 0.5:4 to make sodium peroxydisulfate water-solubleLiquid; After 10:55 fully mixes in mass ratio with water by modified starch, add ammonium persulfate and 50%Sodium persulfate aqueous solution, is warming up to 80～90 DEG C and carries out insulation reaction 0.5～1h; Insulation finishes, and adds ice vinegarAcid, and carry out respectively the sodium persulfate aqueous solution dropping of monomer mixture and other 50%, dropping temperature 80～90 DEG C, control time for adding 1～3h; After reinforced, control 80～90 DEG C of insulation reaction 2～3h of temperature;Be cooled to below 50 DEG C, with 200 order net filtrations, discharging, obtain milky cation phenylpropyl surface sizing agent.Embodiment 6:
Get the tapioca of 14 parts of parts by weight, the hydrogen peroxide of 6 parts, the potassium peroxydisulfate of 0.5 part, the benzene of 8 partsEthene, the butyl acrylate of 5 parts, the glacial acetic acid of 3 parts, the water of 75 parts, the rosin of 2 parts are stand-by; Get propyleneAcid butyl ester, styrene and rosin are for subsequent use after carrying out fully mixing; By potassium peroxydisulfate and water routine 0.5:5 in mass ratioMake persulfate aqueous solution; After by tapioca, 10:50 fully mixes in mass ratio with water, add twoOxygen water and 50% persulfate aqueous solution, be warming up to 80～90 DEG C and carry out insulation reaction 0.5～1h; InsulationFinish, add glacial acetic acid, and carry out respectively the persulfate aqueous solution dropping of monomer mixture and other 50%,80～90 DEG C of dropping temperatures, control time for adding 1～3h; After reinforced, control 80～90 DEG C of guarantors of temperatureTemperature reaction 2～3h; Be cooled to below 50 DEG C, with 200 order net filtrations, discharging, obtain milky cation benzeneThe third Cypres.
Embodiment 7:
Get the modified starch of 10 parts of parts by weight, the ammonium persulfate of 7 parts, the potassium peroxydisulfate, 10 parts of 0.05 partStyrene, the butyl acrylate of 6 parts, the glacial acetic acid of 2 parts, the water of 51 parts and the methacryloxypropyl of 1 partEthyl-trimethyl salmiac is stand-by; For subsequent use after getting butyl acrylate, styrene and carrying out fully mixing; By persulfuric acidPotassium and water in mass ratio routine 0.5:4 are made persulfate aqueous solution; By modified starch and water 10:50 in mass ratioAfter fully mixing, add the persulfate aqueous solution of ammonium persulfate and 50%, be warming up to 80～90 DEG CCarry out insulation reaction 0.5～1h; Insulation finishes, and adds glacial acetic acid and the chlorination of methylacryoyloxyethyl trimethylAmmonium, and carry out respectively the persulfate aqueous solution dropping of monomer mixture and other 50%, dropping temperature 80～90 DEG C, control time for adding 1～3h; After reinforced, control 80～90 DEG C of insulation reaction 2～3h of temperature;Be cooled to below 50 DEG C, with 200 order net filtrations, discharging, obtain milky cation phenylpropyl surface sizing agent.
Claims (10)
1. an environment-friendly type cation phenylpropyl surface sizing agent, is characterized in that, comprises following parts by weightComponent: the dispersant of 10～15 parts, the oxidant of 5～8 parts, the initator, 8～10 parts of 0.05～2 partHard monomer, the soft monomer of 5～8 parts, the acid of 2～3 parts and the water of 50～80 parts, described environment-friendly type cation benzeneThe preparation method of the third Cypres is:
(1) for subsequent use after getting soft, hard monomer or soft, hard monomer and function monomer and carrying out fully mixing;
(2) initator and water are made to initiator solution in routine 0.5:4～6 in mass ratio;
(3) after by dispersant, fully mix 10:50～60 in mass ratio with water, add oxidant and50% initiator solution, is warming up to 80～90 DEG C and carries out insulation reaction 0.5～1h;
(4) insulation finishes, and adds acid or acid and cationic monomer, and carries out respectively monomer mixture and anotherOuter 50% initiator solution drips, and 80～90 DEG C of dropping temperatures are controlled time for adding 1～3h;
(5) after reinforced, control 80～90 DEG C of insulation reaction 2～3h of temperature;
(6) be cooled to below 50 DEG C, with 200 order net filtrations, discharging, obtain milky cation phenylpropyl alcohol tableSurface sizing agent.
2. environment-friendly type cation phenylpropyl surface sizing agent according to claim 1, is characterized in that, alsoComprise the component of following parts by weight: the cationic monomer of the function monomer of 0～3 part and 0～1 part; Described meritCan be mainly rosin by monomer, described cationic monomer is PDDA or methacryloxypropylEthyl-trimethyl salmiac.
3. environment-friendly type cation phenylpropyl surface sizing agent according to claim 1 and 2, is characterized in that,Described dispersant is environment-friendly type cation cassava starch or modified starch.
4. environment-friendly type cation phenylpropyl surface sizing agent according to claim 1 and 2, is characterized in that,Described oxidant is ammonium persulfate or hydrogen peroxide.
5. environment-friendly type cation phenylpropyl surface sizing agent according to claim 1 and 2, is characterized in that,Described initator is ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
6. environment-friendly type cation phenylpropyl surface sizing agent according to claim 1 and 2, is characterized in that,Described hard monomer is styrene.
7. environment-friendly type cation phenylpropyl surface sizing agent according to claim 1 and 2, is characterized in that,Described soft monomer is butyl acrylate.
8. environment-friendly type cation phenylpropyl surface sizing agent according to claim 1 and 2, is characterized in that,Described function monomer is rosin.
9. environment-friendly type cation phenylpropyl surface sizing agent according to claim 1 and 2, is characterized in that,Described acid is glacial acetic acid.
10. the method for the environment-friendly type cation phenylpropyl surface sizing agent described in the above-mentioned arbitrary claim of preparation, itsBe characterised in that, comprise the following steps:
(1) for subsequent use after getting soft, hard monomer or soft, hard monomer and function monomer and carrying out fully mixing;
(2) initator and water are made to initiator solution in routine 0.5:4～6 in mass ratio;
(3) after by dispersant, fully mix 10:50～60 in mass ratio with water, add oxidant and50% initiator solution, is warming up to 80～90 DEG C and carries out insulation reaction 0.5～1h;
(4) insulation finishes, and adds acid or acid and cationic monomer, and carries out respectively monomer mixture and anotherOuter 50% initiator solution drips, and 80～90 DEG C of dropping temperatures are controlled time for adding 1～3h;
(5) after reinforced, control 80～90 DEG C of insulation reaction 2～3h of temperature;
(6) be cooled to below 50 DEG C, with 200 order net filtrations, discharging, obtain milky cation phenylpropyl alcohol tableSurface sizing agent.
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| CN105985499B (en) * | 2015-02-28 | 2018-03-27 | 上海东升新材料有限公司 | It is a kind of to be used to prepare macromolecule emulsifier of cationic rosin size and preparation method thereof |
| CN104846697A (en) * | 2015-04-24 | 2015-08-19 | 杭州百事特实业股份有限公司 | Cation cross-linked styrene-acrylic surface sizing agent and preparation method thereof |
| CN107366186B (en) * | 2017-07-28 | 2021-12-17 | 湖北嘉韵化工科技有限公司 | Preparation method of anti-reversion surface sizing agent |
| JP7188113B2 (en) * | 2018-01-22 | 2022-12-13 | 荒川化学工業株式会社 | Surface emulsion sizing agent for papermaking, method for producing surface emulsion sizing agent for papermaking, and coated paper |
| CN108690169A (en) * | 2018-06-11 | 2018-10-23 | 华东理工大学 | A kind of preparation method of Cypres |
| CN110438838B (en) * | 2019-07-18 | 2021-11-30 | 广东诚铭化工科技有限公司 | Efficient surface sizing agent for paper and preparation method and application thereof |
| CN110356091A (en) * | 2019-08-16 | 2019-10-22 | 福建利树股份有限公司 | A kind of dedicated corrugation facial tissue of freezer |
| CN114163569A (en) * | 2021-12-10 | 2022-03-11 | 上海东升新材料有限公司 | Water-resistant surface sizing agent and preparation method and application thereof |
| CN115094666A (en) * | 2022-01-17 | 2022-09-23 | 广东南隆生物科技有限公司 | Cassava powder combined agent based on papermaking industry and preparation method thereof |
| CN114592376A (en) * | 2022-02-17 | 2022-06-07 | 上海昶法新材料有限公司 | Bio-based surface sizing auxiliary agent, raw material composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649583A (en) * | 2009-09-01 | 2010-02-17 | 东莞市清正合成高新材料有限公司 | Cation surface sizing agent and preparation method thereof |
| CN102127191A (en) * | 2010-12-24 | 2011-07-20 | 江苏富淼科技股份有限公司 | Preparation method of graft copolymer for surface sizing |
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| DE102004027735A1 (en) * | 2004-06-07 | 2005-12-22 | Basf Ag | Finely divided, amphoteric, aqueous polymer dispersions, process for their preparation and their use |
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| CN101649583A (en) * | 2009-09-01 | 2010-02-17 | 东莞市清正合成高新材料有限公司 | Cation surface sizing agent and preparation method thereof |
| CN102127191A (en) * | 2010-12-24 | 2011-07-20 | 江苏富淼科技股份有限公司 | Preparation method of graft copolymer for surface sizing |
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