CN101457499B - Surface sizing agent and its production method - Google Patents
Surface sizing agent and its production method Download PDFInfo
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- CN101457499B CN101457499B CN2007101722823A CN200710172282A CN101457499B CN 101457499 B CN101457499 B CN 101457499B CN 2007101722823 A CN2007101722823 A CN 2007101722823A CN 200710172282 A CN200710172282 A CN 200710172282A CN 101457499 B CN101457499 B CN 101457499B
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- 238000004513 sizing Methods 0.000 title abstract description 38
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract 5
- 239000000839 emulsion Substances 0.000 claims description 54
- 235000004258 Cordia alliodora Nutrition 0.000 claims description 32
- 244000085692 Cordia alliodora Species 0.000 claims description 32
- 239000003999 initiator Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000003643 water by type Substances 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 230000001804 emulsifying effect Effects 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- -1 polyoxyethylene nonylphenol Polymers 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 5
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- BJBSSZXHNOQYAI-UHFFFAOYSA-N [Na].C(CC)S(=O)(=O)O.C(C(=C)C)(=O)OCCO Chemical compound [Na].C(CC)S(=O)(=O)O.C(C(=C)C)(=O)OCCO BJBSSZXHNOQYAI-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical class OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical class CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- ARGZBGBUZXUAHM-UHFFFAOYSA-L potassium sodium hydrogen sulfite sulfooxy sulfate Chemical compound [Na+].[K+].OS([O-])=O.OS(=O)(=O)OOS([O-])(=O)=O ARGZBGBUZXUAHM-UHFFFAOYSA-L 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 33
- 239000003795 chemical substances by application Substances 0.000 abstract description 28
- 239000003995 emulsifying agent Substances 0.000 abstract description 25
- 239000002245 particle Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000004816 latex Substances 0.000 abstract description 5
- 229920000126 latex Polymers 0.000 abstract description 5
- 239000000084 colloidal system Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 abstract 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 31
- 239000003292 glue Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000001254 oxidized starch Substances 0.000 description 16
- 235000013808 oxidized starch Nutrition 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 239000011111 cardboard Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011087 paperboard Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KDFQYGBJUYYWDJ-UHFFFAOYSA-N azane;sodium Chemical compound N.[Na] KDFQYGBJUYYWDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Landscapes
- Paper (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a method for preparing a surface sizing agent for papers. The raw materials used for preparing the surface sizing agent for papers consist of main agents and assistant agents. The main agents are rigid monomers, soft monomers and functional monomers; and the assistant agents are compound emulsifying agents, protective colloids and evocating agents. The proportions of the main agents by weight are as follows: 100 portions of rigid monomers, 40 to 100 portions of soft monomers and 5-40 portions of functional monomers; and the proportions of the assistant agents by weight are as follows: 1 to 10 portions of compound emulsifying agents, 1 to 10 portions of protective colloids and 1 to 8 portions of evocating agents. Compared with the styrene-maleic anhydride surface sizing agent prepared by common emulsifying agents, the surface sizing agent for papers prepared by the method has good mechanical stability, the latex contains no residual emulsifying agents, the particle surface is clean, and no side influence resulted from the emulsifying agents is existed during the sizing and drying process; the surface sizing agent has good membrane forming performance on the paper surface so as to provide excellent water-proof performance and surface flatness for the paper; and the surface sizing agent can increase the stiffness and the smoothness of the paper surface greatly.
Description
Technical field
The present invention relates to a kind of sizing agent and preparation method thereof that shows, be used for the top sizing of paper process paper, to improve the performance that shows of paper, the quality of very high paper belongs to the papermaking chemical product field.
Technical background
Applying glue is one important procedure of papermaking, and purpose is to make paper or cardboard have the performance of resistance liquid (the particularly water and the aqueous solution) diffusion and infiltration.Applying glue can be divided into plasm-glue-blending and top sizing, because the internal sizing agent is subjected to the influence of working condition factors such as (as water quality, pH value, temperature and pumping time) shearings easily; While has proposed requirements at the higher level along with the application of improvement, high speed printing and the high viscosity inks of printing technology to surface strength of paper and profile pattern, and it is unapproachable depending merely on plasm-glue-blending, must carry out top sizing to reach instructions for use to paper.So,,, all to use surface enhancing sizing agent still with the new paper of introducing the production of large-scale paper machine based on wood pulp no matter be paper based on straw pulp with old device fabrication.Top sizing also is a kind of paper surface finishing technology, and except the WATER RESISTANCE that increases paper, deflection, surface strength and the smoothness that can also increase paper are to improve the printing printability.
The surface that present domestic paper industry adopted strengthens sizing agent and is mostly modified starch such as oxidized starch, phosphate ester starch etc., and use PVA (polyvinyl alcohol), CMC (carboxymethyl cellulose) are also arranged.Converted starch is because its cementitiousness is relatively poor, when printing easy hair and powder dropping, cause the scumming phenomenon, do not reach the requirement of high-quality culture printing and newsprint, and the WATER RESISTANCE extreme difference, only on some low-grade paper, use.Though and PVA has film forming and stronger cohesive force preferably, relatively poor because of its WATER RESISTANCE, after the applying glue of cooperation converted starch the degree of sizing that becomes paper is not improved, and become the glossiness behind the paper lower.Because of its price is very high, use amount at home is less at present in addition.CMC (carboxymethyl cellulose) though film forming is preferably also arranged, relatively poor because of WATER RESISTANCE equally, to factor affecting such as the degree of sizing that becomes paper do not improve its extensive application at paper industry.
The synthetic surface sizing agent has become the main flow of Cypres at present, and the synthetic surface sizing agent promptly is to adopt various monomer polymerization reactions to generate macromolecule link thing, can be solution and emulsion.At present with fastest developing speed is cinnamic acrylic ester emulsion-type Cypres.In polymerization process, need to add emulsifying agent.Conventional emulsifier all is to exist in the emulsion to finished product in from the emulsifying stage to the course of reaction always again, is a kind of physics emulsion process.Therefore, remaining a large amount of free emulsifying agents have a strong impact on resistance to water in the product that conventional emulsifier makes, and in film forming procedure, pin hole can occur, influence Surface Sizing Properties.Because the latex particle spacing that conventional emulsifier makes is bigger, the emulsion drying and forming-film time is longer, influences drying efficiency simultaneously.The while emulsifier package overlays on the emulsion particle surface and reduced the emulsion mechanical stability, and is relatively more responsive to ionic environment, increased the probability of breakdown of emulsion.
Disclose (a) among the Chinese patent CN1546792A and in hydrophobic monomer and hydrophilic monomer, added the Cypres preparation method that (b) conventional composite emulsifying agent adds (c) various applying glue promoter, applying glue promoter compounding ingredient and polysiloxanes defoamer, though can improve sizing efficiency, but add the ion complexity that conventional emulsifier and more assistant medicament have increased emulsion, influenced the result of use of sizing agent; In the U.S. Pat 5240771, disclose unsaturated acrylic acid of (a) acrylic acid (b) or acid and joined the Cypres that the emulsion polymerisation of other comonomer of (c) water-soluble monomer (d) (e) polyvinyl alcohol obtains.Though the storage stability and the sizability of this Cypres are better, its chemical stability is lower, in use is easy to breakdown of emulsion, thereby influences its practical application effect.
Summary of the invention
The object of the invention is to provide a kind of new Cypres and preparation method thereof, it can eliminate the negative effect that emulsifying agent residual in the conventional surface sizing agent brings to effect, and the Cypres of producing has that storage stability height, sizing efficiency are good, steady performance in the use.
In order to achieve the above object, the present invention proposes to adopt reactive emulsifier to prepare the new technology of paper surface-sizing agent.Reactive emulsifier has two key groups that can participate in polymerisation, has reactivity and emulsibility concurrently.Its advantage is at emulsifying stage energy emulsified monomer, in polymerization process, can become the part of latex particle with the complete polymerization reaction take place of monomer, not have residual emulsifying agent molecule in the therefore synthetic emulsion, thereby eliminated the adverse effect that conventional emulsifier brings.
According to above-mentioned design, the present invention by the following technical solutions:
A kind of paper adds the sizing agent that the preparation of soft or hard monomer has suitable vitrification point by a certain percentage with Cypres and preparation method thereof; Use reactive emulsifier to prepare the latex particle of surface cleaning, add the film forming that acrylic acid ester function monomer increases emulsion, be equipped with the efficient that some auxiliary materials improve emulsion polymerization simultaneously.Their weight proportion is:
Host: 100 parts of hard monomers
40～100 parts of soft monomers
5～40 parts of function monomers
Assistant agent: 1～10 part of compound emulsifying agent
1～10 part of protecting colloid
1～8 part of initator
It is in vinylacetate, styrene, methyl methacrylate, the acrylonitrile one or more that above-mentioned Cypres prepares used hard monomer.
It is butyl acrylate that above-mentioned Cypres prepares used soft monomer, one or more in methyl acrylate, ethyl acrylate, butyl acrylate, the acrylic acid ethylhexyl.
It is in acrylic acid-2-ethyl caproite, hydroxyethyl methacrylate propane sulfonic acid sodium, the acrylic acid-2-hydroxyl-ethyl ester one or more that above-mentioned Cypres prepares used function monomer.
It is in polyoxyethylene nonylphenol ether, lauryl sodium sulfate, polyoxyethylene nonylphenol ether ammonium sulfate, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, neopelex, the octadecanoic acid ester of polyethylene glycol one or more that above-mentioned Cypres prepares used emulsifying agent.
It is that oxidized form or redox are compound that above-mentioned Cypres prepares used initator, is ammonium persulfate or potassium peroxydisulfate/sodium hydrogensulfite.
Divide following step in the preparation process:
(1) monomer emulsification: a certain amount of main monomer and function monomer are mixed to join in the deionized water of emulsifying agent, under uniform temperature and mixing speed, mix and stir, make emulsified monomer.Main monomer is one or more in vinylacetate, styrene, methyl methacrylate, the acrylonitrile.
(2) preparation seed emulsion: the emulsified monomer of a part is joined in the reactor, add a certain amount of composite initiator, stirring reaction under suitable temperature is up to there being strong blue light to occur
(3) seeded emulsion polymerization: on the seed emulsion particle basis that makes, remaining emulsified monomer and initator be added drop-wise in the reactor on the seed emulsion particle, react.
(4) monomer and initator add the back thermal reacting for two hours, and cooling adds the redox initiator reaction that contains uncle's base alkane then, reduces the conversion ratio that residual monomer increases monomer, adds ammoniacal liquor and regulates the pH value, filters discharging.
This Cypres average grain diameter is 150nm after testing, and mechanicalness and ionic stable has splendid mixcibility mutually with modified starch, can dilute with the water arbitrary proportion, is difficult for breakdown of emulsion, is difficult for flocculation.
Through application testing, the Cypres of this method preparation has good degree of sizing effect, and paper sizing degree and deflection all have rising significantly, and it is good to observe this Cypres filming performance through ESEM (SEM), and the paper surface planarization is good.
The present invention compared with prior art has following conspicuous substantive distinguishing features and advantage:
1. adopt reactive emulsifier to substitute conventional emulsifier: reactive emulsifier carbon-carbon double bonds and hydrophily ion that the present invention uses, in course of reaction, can be attached on the latex particle with the form of monomer reaction with chemical bond, the hydrophily ion dissolves at aqueous phase, thereby improved the water-soluble of emulsion particle, greatly improved the ability that prevents breakdown of emulsion; Also add the good compound use of the high molecular surfactant that has outstanding emulsifying capacity of matching property simultaneously, improve emulsifying capacity.
2. use composite initiator to replace single initator, polymerization reduces the generation of gel at low temperatures.
The redox composite initiator is used in this experiment, and it is few to produce the needed activation evergy of free radical, and the efficiency of initiation height can make the monomer polymerization reaction take place under lower temperature.Therefore being lower than polymerization under the general polymerization temperature, can prevent the generation of implode, also can greatly reduce the generation of gel.
3. add the acrylate functional monomer that is rich in hydroxyl, increase the emulsion film forming performance.
This Cypres can use separately or with the composite use of surface sizing starch, the compound proportion of this Cypres and oxidized starch is 1: 99～20: 80, to paper and paperboard surface applying glue, can increase substantially the ring crush intensity of paper and cardboard, significantly improve the surface strength and the water repelling property of paper and cardboard.Compare with Cypres, the viscosity of this Cypres is less, therefore can stick with paste with oxidized starch and fully mix with vast scale, with this Cypres and the composite use of oxidized starch, find that this Cypres and oxidized starch have synergy, the humidification of cardboard deflection and folding resistance are greater than adding oxidized starch or water-soluble thermosetting resin separately; At compound proportion is can make the paper WATER RESISTANCE reach optimum value at 10: 90 o'clock, and application testing shows that WATER RESISTANCE reaches the like product international most advanced level.Adopting compound scheme can improve the ring crush intensity and the deflection of cardboard on the one hand, can reduce the cost of Cypres on the other hand, improve the competitiveness of product in market.
The specific embodiment
Preparation embodiment one: in the vial that thermometer, agitator are housed, add 10 parts of polyoxyethylene nonyl phenyl alkene ethers and 150 parts of deionized waters at 50 ℃ of stirring 20min.Slowly add 100 parts of vinylacetates, 40 parts of butyl acrylates and 10 parts of acrylic acid ethylhexyls again, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion; Add 4 parts of ammonium persulfates and 40 parts of deionized waters mixing stirring formation initiator solutions; In the four-hole reaction bulb of the logical nitrogen that agitator, dropping funel, thermometer are housed, add 300 parts 50 ℃ deionized water, 2 parts of polyvinyl alcohol, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 70 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add.Insulation 45min after reaction is finished, being cooled to 45 ℃ of an amount of ammoniacal liquor adjusting pH values of adding is 6.8～7.0, filters discharging and gets final product.
Preparation embodiment two: in the vial that thermometer, agitator are housed, add 8 parts of lauryl sodium sulfate and 180 parts of deionized waters at 50 ℃ of stirring 20min.Slowly add 100 parts of styrene, 70 parts of methyl acrylates and 35 parts of hydroxyethyl methacrylate propane sulfonic acid sodium again, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion; Add 2 parts of ammonium persulfates and 40 parts of deionized waters mixing stirring formation initiator solutions; Deionized water, 5 parts of polyvinyl alcohol of in the four-hole reaction bulb of the logical nitrogen that agitator, dropping funel, thermometer are housed, adding 400 parts 50 ℃, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 70 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add.Insulation 45min after reaction is finished, being cooled to 45 ℃ of an amount of ammoniacal liquor adjusting pH values of adding is 6.8～7.0, filters discharging and gets final product.
Preparation embodiment three: in the vial that thermometer, agitator are housed, add 4 parts of neopelexes and 200 parts of deionized waters at 50 ℃ of stirring 20min.Slowly add 100 parts of methyl methacrylates, 90 parts of ethyl acrylates and 20 parts of hydroxyethyl methacrylate propane sulfonic acid sodium again, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion; Add 8 parts of potassium peroxydisulfates and 40 parts of deionized waters mixing stirring formation initiator solutions; In the four-hole reaction bulb of the logical nitrogen that agitator, dropping funel, thermometer are housed, add 400 parts 50 ℃ deionized water, 2 parts of polyvinyl alcohol, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 70 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add.Insulation 45min after reaction is finished, being cooled to 45 ℃ of an amount of ammoniacal liquor adjusting pH values of adding is 6.8～7.0, filters discharging and gets final product.
Preparation embodiment four: in the vial that thermometer, agitator are housed, add 2 parts of polyoxyethylene nonylphenol ether ammonium sulfate and 170 parts of deionized waters at 50 ℃ of stirring 20min.Slowly add 100 parts of acrylonitrile, 70 parts of acrylic acid ethylhexyls and 5 parts of acrylic acid-2-hydroxyl-ethyl esters again, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion; Add 3 parts of potassium hydrogen persulfate-pentathionic acid ammonia sodium and 40 parts of deionized waters mixing stirring formation initiator solutions; In the four-hole reaction bulb of the logical nitrogen that agitator, dropping funel, thermometer are housed, add 400 parts 50 ℃ deionized water, 10 parts of polyvinyl alcohol, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 65 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add.Insulation 45min after reaction is finished, being cooled to 45 ℃ of an amount of ammoniacal liquor adjusting pH values of adding is 6.8～7.0, filters discharging and gets final product.
Preparation embodiment five: in the vial that thermometer, agitator are housed, add 5 parts of lauryl sodium sulfate and 180 parts of deionized waters at 50 ℃ of stirring 20min.Slowly add 100 parts of vinylacetates, 70 parts of methyl acrylates and 10 parts of acrylic acid-2-ethyl caproites again, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion; Add 3 parts of potassium peroxydisulfate-sodium hydrogensulfite composite initiators and 40 parts of deionized waters mixing stirring formation initiator solutions; In the four-hole reaction bulb of the logical nitrogen that agitator, dropping funel, thermometer are housed, add 400 parts 50 ℃ deionized water, 8 parts of polyvinyl alcohol, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 70 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add.Insulation 45min after reaction is finished, being cooled to 45 ℃ of an amount of ammoniacal liquor adjusting pH values of adding is 6.8～7.0, filters discharging and gets final product.
Application example one: preparation concentration is 8% oxidized starch paste, and the concentration by 1.5% adds the synthetic surface sizing agent, 45 ℃ of stirrings surface glue is fully mixed in oxidized starch is stuck with paste
Using no internal sizing body paper paper to carry out the applying glue experiment, quantitatively is 83.49g/m2,, its water repelling property such as table 1
| Test specimens | Blank sample | Oxidized starch | Method 1 | Import glue |
| Degree of sizing (s) | 0 | 5 | 66 | 59 |
To white board Zhang Jinhang top sizing, quantitatively be 147g/m2, deflection and ring crush intensity index such as table 2
| Test performance | Deflection (uNm) | Ring crush index (Nmg-1) |
| Blank sample | 86 | 12.08 |
| Oxidized starch | 100 | 12.20 |
| Method 1 | 131 | 12.76 |
| Import glue | 122 | 12.40 |
Application example two: the Cypres that has different glass temperature (Tg) by example one preparation, preparation concentration is 5% oxidized starch paste, the synthetic surface applying glue liquid that adds the Cypres preparation variable concentrations of different amounts, 45 ℃ of stirrings surface glue in sticking with paste, is fully mixed oxidized starch, use no internal sizing body paper paper to carry out the applying glue experiment, be 83.49g/m2 quantitatively, its water repelling property such as table 3
| Sizing agent concentration | 0.50％ | ?1.00％ | ?1.50％ | ?2.00％ | ?2.50％ |
| Tg＝7.4℃ | 35 | ?90 | ?90 | ?84 | ?81 |
| Tg＝35℃ | 91 | ?120 | ?118 | ?115 | ?110 |
Application example three: press example one preparation Cypres, preparation concentration is 10% oxidized starch paste, concentration by 1.0% adds the synthetic surface sizing agent, 45 ℃ of stirrings surface glue in sticking with paste, is fully mixed oxidized starch, use no internal sizing body paper paper to carry out the applying glue experiment, be 83.49g/m2 quantitatively, test paper folding strength.The research surface, folding is 5 times after the applying glue of pure zirconia starch, sticks with paste mixing application folding 8 times with self-control Cypres and oxidized starch, sticks with paste mixing application folding 4 times with import glue and oxidized starch.
Claims (4)
1. paper Cypres, the raw materials used and process of its preparation is:
Thermometer is being housed, add 10 parts of polyoxyethylene nonylphenol ether and 150 parts of deionized waters in the vial of agitator at 50 ℃ of stirring 20min, slowly add 100 parts of vinylacetates again, 40 parts of butyl acrylates and 10 parts of acrylic acid ethylhexyls, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion, add 4 parts of ammonium persulfates and 40 parts of deionized waters mixing stirring formation initiator solutions, agitator is being housed, dropping funel, the deionized water that adds 300 parts 50 ℃ in the four-hole reaction bulb of the logical nitrogen of thermometer, 2 parts of polyvinyl alcohol, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 70 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add, insulation 45min after reaction is finished, be cooled to 45 ℃, adding an amount of ammoniacal liquor adjusting pH value is 6.8～7.0, filters discharging and gets final product.
2. paper Cypres, the raw materials used and process of its preparation is:
Thermometer is being housed, add 8 parts of lauryl sodium sulfate and 180 parts of deionized waters in the vial of agitator at 50 ℃ of stirring 20min, slowly add 100 parts of styrene again, 70 parts of methyl acrylates and 35 parts of hydroxyethyl methacrylate propane sulfonic acid sodium, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion, add 2 parts of ammonium persulfates and 40 parts of deionized waters mixing stirring formation initiator solutions, agitator is being housed, dropping funel, the deionized water that adds 400 parts 50 ℃ in the four-hole reaction bulb of the logical nitrogen of thermometer, 5 parts of polyvinyl alcohol, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 70 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add, insulation 45min after reaction is finished, be cooled to 45 ℃, adding an amount of ammoniacal liquor adjusting pH value is 6.8～7.0, filters discharging and gets final product.
3. paper Cypres, the raw materials used and process of its preparation is:
Thermometer is being housed, add 4 parts of neopelexes and 200 parts of deionized waters in the vial of agitator at 50 ℃ of stirring 20min, slowly add 100 parts of methyl methacrylates again, 90 parts of ethyl acrylates and 20 parts of hydroxyethyl methacrylate propane sulfonic acid sodium, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion, add 8 parts of potassium peroxydisulfates and 40 parts of deionized waters mixing stirring formation initiator solutions, agitator is being housed, dropping funel, the deionized water that adds 400 parts 50 ℃ in the four-hole reaction bulb of the logical nitrogen of thermometer, 2 parts of polyvinyl alcohol, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 70 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add, insulation 45min after reaction is finished, be cooled to 45 ℃, adding an amount of ammoniacal liquor adjusting pH value is 6.8～7.0, filters discharging and gets final product.
4. paper Cypres, the raw materials used and process of its preparation is:
Thermometer is being housed, add 5 parts of lauryl sodium sulfate and 180 parts of deionized waters in the vial of agitator at 50 ℃ of stirring 20min, slowly add 100 parts of vinylacetates again, 70 parts of methyl acrylates and 10 parts of acrylic acid-2-ethyl caproites, progressively improve mixing speed stirring and emulsifying 1h and make pre-emulsion, add 3 parts of potassium peroxydisulfate-sodium hydrogensulfite composite initiators and 40 parts of deionized waters mixing stirring formation initiator solutions, agitator is being housed, dropping funel, the deionized water that adds 400 parts 50 ℃ in the four-hole reaction bulb of the logical nitrogen of thermometer, 8 parts of polyvinyl alcohol, 15% pre-emulsion and 10% initiator solution, continue to add thermal agitation and be warming up to 70 ℃, react when blue light appears in emulsion, begin to drip remaining pre-emulsion and initiator solution, be controlled in the 2h and add, insulation 45min after reaction is finished, be cooled to 45 ℃, adding an amount of ammoniacal liquor adjusting pH value is 6.8～7.0, filters discharging and gets final product.
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| CN102321416B (en) * | 2011-08-09 | 2014-03-19 | 海南必凯水性涂料有限公司 | Preparation method of self-adhesive acrylic acid paint for coating |
| CN102898970B (en) * | 2012-11-02 | 2014-10-08 | 绍兴振德医用敷料有限公司 | Method for preparing ultraviolet light polymerization environment-friendly antibacterial acrylic ester medical pressure sensitive adhesive product |
| CN103696319B (en) * | 2013-12-24 | 2017-06-30 | 南昌大学 | A kind of paper pallet of surface chemistry reinforcing and preparation method thereof |
| CN103866626B (en) * | 2014-02-28 | 2016-06-29 | 新昌县澄潭镇博纳机械厂 | A kind of arabic gum sizing agent and preparation method thereof |
| CN103881625A (en) * | 2014-02-28 | 2014-06-25 | 成都中节能反光材料有限公司 | Water-based adhesive for highly bright reflective transfer film and preparation process of adhesive |
| CN105732875A (en) * | 2016-02-28 | 2016-07-06 | 吉林建筑大学 | Multifunctional quaternary soap-free vinyl acetate-acrylic emulsion and preparation method thereof |
| CN112941956A (en) * | 2021-03-23 | 2021-06-11 | 南京师范大学 | Surface sizing agent for improving stiffness of vegetable fiber packaging lunch box and preparation method thereof |
| CN114045702B (en) * | 2021-11-18 | 2023-05-26 | 广东科力德新材料有限公司 | Polymer emulsion capable of recycling and degrading PE (polyethylene) paper laminated film |
| CN116732821A (en) * | 2023-07-03 | 2023-09-12 | 山东仁丰特种材料股份有限公司 | Method for producing gluing type medical dialysis base paper by using fourdrinier vat paper machine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5240771A (en) * | 1990-04-02 | 1993-08-31 | Basf Aktiengesellschaft | Copolymers based on C1 -C8 -alkyl acrylates and/or methacrylates and preparation and use thereof |
| EP0763628A1 (en) * | 1995-04-03 | 1997-03-19 | Arakawa Kagaku Kogyo Kabushiki Kaisha | Papermaking rosin emulsion size and method of paper sizing with the same |
| CN1509311A (en) * | 2002-03-15 | 2004-06-30 | ̫ƽ����֬��˾ | Styrene-acrylate copolymer composition suitable for surface size |
| CN1546792A (en) * | 2003-12-05 | 2004-11-17 | 北京清大华创科技发展有限公司 | Preparation method of glue blending agent for paper making |
-
2007
- 2007-12-14 CN CN2007101722823A patent/CN101457499B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5240771A (en) * | 1990-04-02 | 1993-08-31 | Basf Aktiengesellschaft | Copolymers based on C1 -C8 -alkyl acrylates and/or methacrylates and preparation and use thereof |
| EP0763628A1 (en) * | 1995-04-03 | 1997-03-19 | Arakawa Kagaku Kogyo Kabushiki Kaisha | Papermaking rosin emulsion size and method of paper sizing with the same |
| CN1509311A (en) * | 2002-03-15 | 2004-06-30 | ̫ƽ����֬��˾ | Styrene-acrylate copolymer composition suitable for surface size |
| CN1546792A (en) * | 2003-12-05 | 2004-11-17 | 北京清大华创科技发展有限公司 | Preparation method of glue blending agent for paper making |
Non-Patent Citations (2)
| Title |
|---|
| 李建文 等.高浓低泡阳离子表面施胶剂的合成及性能研究.《中国造纸》.2006,第25卷(第11期),28-31. * |
| 詹新岭 等.合成聚合物表面施胶剂的最新研究进展.《上海造纸》.2006,第37卷(第5期),42-48. * |
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