CN101333790B - Modified petroleum resin sizing agent, preparation method and application thereof - Google Patents
Modified petroleum resin sizing agent, preparation method and application thereof Download PDFInfo
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- CN101333790B CN101333790B CN2008100483980A CN200810048398A CN101333790B CN 101333790 B CN101333790 B CN 101333790B CN 2008100483980 A CN2008100483980 A CN 2008100483980A CN 200810048398 A CN200810048398 A CN 200810048398A CN 101333790 B CN101333790 B CN 101333790B
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Abstract
Disclosed is a modified petroleum resin sizing agent, containing: a modified petroleum resin; a dispersing agent which is a compound system including at least one cationic surfactant and at least one nonionic surfactant; and a retention and drainage agent which includes at least one cationic polymer, at least one metal, at least one salt and olefin. A preparation method thereof comprises: adding a modifier into the petroleum resin for reaction for three to four hours at a temperature between 190 and 200 DEG C, then adding the retention and drainage agent and the dispersing agent into the modified petroleum resin for stirring, and making the mixture enter a homogenizer machine for obtaining the modified petroleum resin sizing agent by homogenization, cooling and filtration. The modified petroleum resin sizing agent has the advantages of simple process, easy operation, easy retention of paper sizing by prepared sizing agent, strong retention properties, enhanced intensity of finished paper, reduced corrosion of equipment and extended service life of the paper machine.
Description
Technical field
The present invention relates to modified petroleum resin sizing agent and its production and use, belong to chemical technology field.
Background technology
The used neutral sizing agent of paper sizing mainly contains the rosin based sizing agent in the market, alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA).Use the AKD applying glue to have the defective that applying glue hysteresis, page skid and the applying glue expense is high; ASA is hydrolysis very easily, needs on-the-spot emulsification during applying glue, has the higher deficiency of technological requirement; Though cation colophony glue has overcome the shortcoming of AKD and ASA, equipment investment is big, and process conditions require tight, and the preparation difficulty is big, and natural rosin rise in price in addition uses the cost of cation colophony glue higher.Petropols are because of its abundant raw material, cheap, with the existing many pieces of patent reports of the sizing agent of its modifier preparation.
Application number 94103908.0, publication number CN 1109489A.This invention new dispersant that a kind of sizing agent that has premium properties in from acid range to neutral range uses is provided and from acid range to neutral range in have the new manufacture method of the sizing agent of good sizability.The dispersant of this method preparation is a water-soluble graft polymers, and generated time is long, and emulsification need be used pressurized equipment.
Application number 97105831.8, publication number CN 1163330A.It is the preparation method of the sizing agent for paper of main raw material with Petropols that this patent of invention discloses a kind of, modification C
9Add rosin in the Petropols, rare earth halide, alkali formula sodium acetate, paraffin, oleic acid refluxes, and gets semi-finished product; Add 3～5% solid sodium hydroxide (potassium) and 0.3～0.5% hydramine in the water, stir in the time of 98～102 ℃ and add semi-finished product 30～50%, reflux, the liquid petroleum resin cementing agent.This method technology is simple, easy operating, but return time grows (9～13h) in the preparation process.
Patent No. ZL 02111259.2, publication number CN 1448436A, notification number CN 1180021C.This patent of invention discloses a kind of preparation method of petroleum resin emulsion, Petropols are carbon five, C 9 petroleum resin or carbon five, carbon nine copolymerized petroleum resins, its softening point is 60～120 ℃, this method may further comprise the steps: make both fully mix formation solution with adding oleic acid after the Petropols fusion, the weight ratio of Petropols and oleic acid is 8～12: 1; To the above-mentioned concentration that adds while stirring is that 5～15wt% and temperature are that 90～100 ℃ the monoethanolamine aqueous solution makes it emulsification, emulsifying temperature is 85～100 ℃, emulsification times is 30～180 minutes, and the addition of the monoethanolamine aqueous solution is to determine at 3～4: 1 with the mol ratio of oleic acid and monoethanolamine; Filter after the above-mentioned emulsion cooling the petroleum resin emulsion product.The petroleum resin emulsion average grain diameter of this method preparation has good stable below 0.5 micron, and preparation process and use do not produce foam substantially, but emulsifying temperature height in the preparation process need be made troubles to operation with 98 ℃ hot water during dispersion.
Technical field
The present invention seeks to overcome the deficiencies in the prior art, a kind of modified petroleum resin sizing agent and preparation method are provided, this method technology is simple, easy operating, the sizing agent of preparation are used for paper sizing easily to be kept, and the retention performance is strong, can increase paper strength, reduce equipment corrosion, prolong the paper machine life-span.
The technical scheme that the present invention addresses the above problem is as follows:
A kind of modified petroleum resin sizing agent comprises: modified petroleum resin (A); Dispersant (B) comprises the compound system of at least a cationic surfactant and at least a non-ionic surface active agent; Retention and drainage aid agent (C) comprises at least a cationic polymer, at least a salt and the paraffin of at least a metal.
The mass ratio of the consumption sum of the consumption of above-mentioned modified petroleum resin and dispersant and retention and drainage aid agent [be A:(B+C)] be 50～1: 1; The consumption mass ratio of dispersant and retention and drainage aid agent is 20～1: 1.
The consumption mass ratio of cationic surfactant and non-ionic surface active agent is 6～1: 3 in the above-mentioned dispersant; The consumption mass ratio of cationic polymer, slaine and paraffin is 10～20 in the retention and drainage aid agent: 1: 2.5～5.
Described modified petroleum resin is obtained by Petropols and modifier reaction, adds modifier in Petropols, and 190～200 ℃ of reaction 3～4h get modified petroleum resin, and wherein the consumption mass ratio of Petropols and modifier is 10～20: 1; It is 60～95 ℃ C that described Petropols are selected from softening point
5Petropols, C
9Petropols or C
5And C
9Copolymerized petroleum resin, modifier are selected from maleic anhydride, maleic acid, fumaric acid, crotonic acid or furoate clothing; Preferred maleic anhydride.
Described cationic surfactant is at least a in amine salt type surfactant or the quaternary ammonium salt cationic surfactant, and amine salt type surfactant is as primary amine salt, secondary amine salt, tertiary ammonium salt type surfactant, hydroxylamine, diamines or polyamines, the amine that contains acyl group, guanidine derivatives; The quaternary ammonium salt cationic surfactant that can enumerate has: Dodecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, cetalkonium chloride, stearyl dimethyl benzyl ammonium chloride, hexadecyldimethyl benzyl ammonium allyl ammonium chloride, chlorination N, N-dimethyl-N-benzyl-3-(stearoyl amido) propylamine, dibenzyl two (stearamide ethyl) ammonium chloride etc.Preferred quaternary ammonium salt cationic surfactant, more preferably zephiran.Non-ionic surface active agent such as fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, alkanolamide, polyethenoxy alkanolamide etc.The preferred alkyl phenol polyethenoxy ether more preferably has the alkyl of 8～10 carbon atoms.
0.2～20% of the preferred modified petroleum resin quality of consumption of dispersant (B), more preferably 0.5～10% of the modified petroleum resin quality.
Described cationic polymer is at least a in the graft copolymer of cationic modified starch, cationic polyacrylamide, cationic polyacrylate, starch, acrylamide.The graft copolymer of preferred cationic modified starch, starch and acrylamide.5～30% of the preferred modified petroleum resin quality of the consumption of the graft copolymer of cationic modified starch, starch and acrylamide, more preferably 10～25% of the modified petroleum resin quality.
Slaine comprises the salt that IA, IIA in the periodic table or IIIA metal form.Preferred IIIA slaine, more preferably aluminium salt, suitable aluminium salt can be aluminium polychloride, aluminium chloride, basic aluminium acetate, hydrazine aluminum sulfate.0.2～8% of the preferred modified petroleum resin quality of the consumption of aluminium salt, more preferably 0.2～5% of the modified petroleum resin quality.8～15% of the preferred modified petroleum resin quality of the consumption of paraffin, more preferably 10～12% of the modified petroleum resin quality.
The present invention also provides the preparation method of above-mentioned modified petroleum resin sizing agent: add modifier in Petropols, 190～200 ℃ of reaction 3～4h get modified petroleum resin, modified petroleum resin is cooled to 100～140 ℃, adds retention and drainage aid agent, dispersant, stir 30～60min; Enter homogenizer, homogeneous 1～3h is cooled to room temperature, filters promptly to get modified petroleum resin sizing agent.
The application of modified petroleum resin sizing agent of the present invention in paper sizing.Modified petroleum resin sizing agent of the present invention is a milky white liquid, solid content 30～45wt%, and pH=3～4, the cold water dilution gets final product during use.
Technology of the present invention is simple, and easy operating, the sizing agent of preparation compared with prior art have following characteristics:
1, neutrality is copied paper, can increase paper strength, reduces equipment corrosion, prolongs the paper machine life-span.
2, easily keep, the retention performance is strong, can keep fiber fines and filler in the slurry, saves the slurry consumption, reduces cost.
3, glue-applying technique is simple, and is applied widely, during application its dilution stirred and can use.
Concrete embodiment:
Below further describe details of the present invention by some examples, but embodiment and do not mean that limitation of the present invention.
Embodiment 1
With 98 parts of (quality, down together) C
5/ C
9Copolymerized petroleum resin and 190～200 ℃ of reactions of 5 parts of maleic anhydrides 4h get modified petroleum resin.Be cooled to 120 ℃, add 10.4 parts of paraffin, 0.5 part of aluminium polychloride, 3.8 parts of stearyl dimethyl benzyl ammonium chloride/polyoxyethylene nonylphenol ether compound emulsifying agents (2: 3, mass ratio) stir 30min.Enter homogenizer, add 12 parts of cationic modified starchs, homogeneous 45min adds entry, continues homogeneous 1h, is cooled to room temperature, filters and promptly gets modified petroleum resin sizing agent.
Measure product solid content, stability, pH and average grain diameter, the results are shown in Table one.
Embodiment 2
With 95 parts of C
5/ C
9Copolymerized petroleum resin and 190～200 ℃ of reactions of 5 parts of maleic anhydrides 4h get modified petroleum resin.Be cooled to 120 ℃, add 8.6 parts of paraffin, 0.6 part of aluminium polychloride, 6.5 parts of cetalkonium chloride/polyoxyethylene nonylphenol ether compound emulsifying agents (5: 6, mass ratio) stir 45min.Enter homogenizer, add the graft copolymer of 16 parts of starch and acrylamide, homogeneous 30min adds entry, continues homogeneous 2h, is cooled to room temperature, filters and promptly gets modified petroleum resin sizing agent.
Measure product solid content, stability, pH and average grain diameter, the results are shown in Table one.
Embodiment 3
With 105 parts of C
9Petropols and 190～200 ℃ of reactions of 6 parts of maleic anhydrides 4h get modified petroleum resin.Be cooled to 110 ℃, add 12.4 parts of paraffin, 0.5 part of basic aluminium acetate, 6.8 parts of stearyl dimethyl benzyl ammonium chloride/polyoxyethylene nonylphenol ether compound emulsifying agents (2: 3, mass ratio) stir 60min.Enter homogenizer, add the graft copolymer of 18 parts of starch and acrylamide, homogeneous 45min adds entry, continues homogeneous 1h, is cooled to room temperature, filters and promptly gets modified petroleum resin sizing agent.
Measure product solid content, stability, pH and average grain diameter, the results are shown in Table one.
Embodiment 4
With 100 parts of C
9Petropols and 190～200 ℃ of reactions of 5 parts of maleic anhydrides 4h get modified petroleum resin.Be cooled to 100 ℃, add 12.8 parts of paraffin, 0.8 part of basic aluminium acetate, 10.2 parts of cetalkonium chloride/polyoxyethylene nonylphenol ether compound emulsifying agents (5: 6, mass ratio) stir 60min.Enter homogenizer, add 12 parts of cationic modified starchs, homogeneous 30min adds entry, continues homogeneous 2h, is cooled to room temperature, filters and promptly gets modified petroleum resin sizing agent.
Measure product solid content, stability, pH and average grain diameter, the results are shown in Table one.
Embodiment 5
With 98 parts of C
5/ C
9Copolymerized petroleum resin and 190～200 ℃ of reactions of 5 parts of fumaric acid 4h get modified petroleum resin.Be cooled to 120 ℃, add 10.4 parts of paraffin, 0.5 part of aluminium polychloride, 3.8 parts of stearyl dimethyl benzyl ammonium chloride/OPEO compound emulsifying agents (2: 3, mass ratio) stir 30min.Enter homogenizer, add 12 parts of cationic modified starchs, homogeneous 30min adds entry, continues homogeneous 2h, is cooled to room temperature, filters and promptly gets modified petroleum resin sizing agent.
Measure product solid content, stability, pH and average grain diameter, the results are shown in Table one.
Embodiment 6
With 95 parts of C
9Petropols and 190～200 ℃ of reactions of 5 parts of fumaric acid 4h get modified petroleum resin.Be cooled to 120 ℃, add 8.6 parts of paraffin, 0.6 part of basic aluminium acetate, 8.5 parts of cetalkonium chloride/OPEO compound emulsifying agents (5: 6, mass ratio) stir 30min.Enter homogenizer, add the graft copolymer of 16 parts of starch and acrylamide, homogeneous 45min adds entry, continues homogeneous 2h, is cooled to room temperature, filters and promptly gets modified petroleum resin sizing agent.
Measure product solid content, stability, pH and average grain diameter, the results are shown in Table one.
Embodiment 7
With 105 parts of C
9Petropols and 190～200 ℃ of reactions of 4 parts of fumaric acid 4h get modified petroleum resin.Be cooled to 100 ℃, add 12.4 parts of paraffin, 0.5 part of basic magnesium carbonate, 6.8 parts of stearyl dimethyl benzyl ammonium chloride/OPEO compound emulsifying agents (2: 3, mass ratio) stir 30min.Enter homogenizer, add 18 parts of cationic polyacrylates, homogeneous 45min adds entry, continues homogeneous 1h, is cooled to room temperature, filters and promptly gets modified petroleum resin sizing agent.
Measure product solid content, stability, pH and average grain diameter, the results are shown in Table one.
Embodiment 8
With 100 parts of C
9Petropols and 190～200 ℃ of reactions of 8 parts of fumaric acid 4h get modified petroleum resin.Be cooled to 140 ℃, add 12.8 parts of paraffin, 0.8 part of alkali formula sodium acetate, 4.2 parts of dodecyl benzyl dimethyl ammonium chloride/OPEO compound emulsifying agents (1: 1, mass ratio) stir 45min.Enter homogenizer, add 10 parts of polyacrylamides, homogeneous 45min adds entry, continues homogeneous 2h, is cooled to room temperature, filters and promptly gets modified petroleum resin sizing agent.
Measure product solid content, stability, pH and average grain diameter, the results are shown in Table one.
Table one
| Solid content (%) | Stability | The pH value | Average grain diameter (μ m) | |
| Embodiment 1 | 30 | Not stratified | 3 | 0.35 |
| Embodiment 2 | 35 | Not stratified | 3 | 0.45 |
| Embodiment 3 | 45 | Not stratified | 4 | 0.48 |
| Embodiment 4 | 40 | Not stratified | 4 | 0.32 |
| Embodiment 5 | 30 | Not stratified | 3 | 0.38 |
| Embodiment 6 | 30 | Not stratified | 4 | 0.43 |
| Embodiment 7 | 35 | Not stratified | 4 | 0.55 |
| Embodiment 8 | 35 | Not stratified | 4 | 0.58 |
Annotate:
1. solid content is by GB GB2793 standard test;
2. stability is by at room temperature leaving standstill 30 days, and range estimation has or not the sedimentation layering;
3.pH value is measured with common pH test paper;
4. average grain diameter employing electron microscope is got according to method and is recorded.
Claims (4)
1. a modified petroleum resin sizing agent comprises: modified petroleum resin; Dispersant comprises the compound system of at least a cationic surfactant and at least a non-ionic surface active agent; Retention and drainage aid agent comprises at least a cationic polymer, at least a salt and the paraffin of at least a metal; And made by laxative remedy: add modifier in Petropols, 190～200 ℃ of reaction 3～4h get modified petroleum resin, and modified petroleum resin is cooled to 100～140 ℃, add retention and drainage aid agent, dispersant, stir 30～60min; Enter homogenizer, homogeneous 1～3h is cooled to room temperature, filters promptly to get modified petroleum resin sizing agent; Described cationic polymer is at least a in the graft copolymer of cationic modified starch, cationic polyacrylamide, cationic polyacrylate, starch, acrylamide; At least a salt of at least a metal comprises the salt that IA, IIA in the periodic table or IIIA metal form; The mass ratio of the consumption sum of the consumption of modified petroleum resin and dispersant and retention and drainage aid agent is 50～1: 1 in the modified petroleum resin sizing agent; The consumption mass ratio of dispersant and retention and drainage aid agent is 20～1: 1; The consumption mass ratio of cationic surfactant and non-ionic surface active agent is 6～1: 3 in the dispersant; The consumption mass ratio of at least a salt of cationic polymer, at least a metal and paraffin is 10～20 in the retention and drainage aid agent: 1: 2.5～5; The consumption mass ratio that wherein prepares modified petroleum resin PetroChina Company Limited. resin and modifier is 10～20: 1; It is 60～95 ℃ C that described Petropols are selected from softening point
5Petropols, C
9Petropols or C
5And C
9Copolymerized petroleum resin, modifier are selected from maleic anhydride, maleic acid, fumaric acid, crotonic acid or furoate clothing.
2. modified petroleum resin sizing agent according to claim 1, it is characterized in that: described cationic surfactant is at least a in amine salt type surfactant or the quaternary ammonium salt cationic surfactant, and non-ionic surface active agent is at least a in fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene carboxylate, alkanolamide, the polyethenoxy alkanolamide.
3. the preparation method of claim 1 or 2 described modified petroleum resin sizing agents, it is characterized in that: in Petropols, add modifier, 190～200 ℃ of reaction 3～4h get modified petroleum resin, modified petroleum resin is cooled to 100～140 ℃, add retention and drainage aid agent, dispersant, stir 30～60min; Enter homogenizer, homogeneous 1～3h is cooled to room temperature, filters promptly to get modified petroleum resin sizing agent.
4. claim 1 or 2 application of described modified petroleum resin sizing agent in paper sizing.
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| CN102153710B (en) * | 2011-05-06 | 2012-11-07 | 上虞市佳华高分子材料有限公司 | Preparation method of modified petroleum resin |
| CN102704338B (en) * | 2012-05-08 | 2014-07-02 | 华南理工大学 | Sizing reinforcing agent and preparation process and application thereof |
| CN103147349B (en) * | 2013-03-22 | 2016-01-20 | 杭州百事特实业股份有限公司 | A kind of high molecular polymerization Petropols class Cypres |
| CN110409217A (en) * | 2018-04-27 | 2019-11-05 | 上海东升新材料有限公司 | A kind of strong paper surface sizing agent of high table |
| CN109594414A (en) * | 2018-12-05 | 2019-04-09 | 贵州众旺包装有限公司 | A kind of sizing agent of wrapping paper and preparation method thereof |
| CN109487619A (en) * | 2018-12-05 | 2019-03-19 | 贵州众旺包装有限公司 | A kind of sizing agent of wrapping paper |
| CN112300407B (en) * | 2020-10-27 | 2024-04-26 | 安徽同心新材料科技有限公司 | High-solid-content water-based petroleum resin emulsion and preparation method thereof |
| CN115058919A (en) * | 2022-06-30 | 2022-09-16 | 济宁明升新材料有限公司 | Preparation method of rosin substitute/cationic rosin sizing agent |
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