CN104744663A - Waste leather collagen modified polyurethane papermaking sizing agent and preparation method thereof - Google Patents
Waste leather collagen modified polyurethane papermaking sizing agent and preparation method thereof Download PDFInfo
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- 102000008186 Collagen Human genes 0.000 title claims abstract description 60
- 108010035532 Collagen Proteins 0.000 title claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 58
- 229920001436 collagen Polymers 0.000 title claims abstract description 56
- 238000004513 sizing Methods 0.000 title claims abstract description 52
- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010985 leather Substances 0.000 title claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004970 Chain extender Substances 0.000 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 13
- 238000004945 emulsification Methods 0.000 claims abstract description 12
- -1 polyol compound Chemical class 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical group OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims 2
- ZNXHWPFMNPRKQA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 ZNXHWPFMNPRKQA-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
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- 230000002194 synthesizing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种废皮胶原蛋白改性聚氨酯型造纸施胶剂及其制备方法，该方法利用从废弃革屑中提取的胶原蛋白对聚氨酯进行改性，制得一种造纸表面施胶剂。包括以下步骤：(1)预聚体的制备：异氰酸酯与多元醇化合物制得聚氨酯预聚体；(2)预聚体的扩链：产物中加入亲水扩链剂，加入胶原蛋白和适量丙酮，反应得到淡黄色透明产物；(3)预聚体的中和：加入中和剂中和，快速搅拌混合；(4)乳化：加入一定量蒸馏水乳化，制得一种废皮胶原蛋白改性聚氨酯型造纸施胶剂乳液。本发明在合成聚氨酯水乳液过程中添加从废弃皮革中提取的胶原蛋白进行改性，开发出了一种新型造纸助剂，在减少固体废弃物的同时，也得到了相应的经济效益。The invention discloses a waste skin collagen modified polyurethane type papermaking sizing agent and a preparation method thereof. The method utilizes collagen extracted from waste leather shavings to modify polyurethane to prepare a papermaking surface sizing agent . The method comprises the following steps: (1) preparation of prepolymer: isocyanate and polyol compound to prepare polyurethane prepolymer; (2) chain extension of prepolymer: adding hydrophilic chain extender to the product, adding collagen and appropriate amount of acetone , react to obtain light yellow transparent product; (3) neutralization of prepolymer: add neutralizer to neutralize, stir and mix quickly; (4) emulsification: add a certain amount of distilled water to emulsify, and make a modified waste skin collagen Polyurethane paper sizing agent emulsion. In the process of synthesizing polyurethane aqueous emulsion, the collagen extracted from waste leather is added for modification, and a new type of papermaking auxiliary agent is developed. While reducing solid waste, the invention also obtains corresponding economic benefits.
Description
技术领域technical field
本发明涉及聚氨酯应用领域，具体涉及一种废皮胶原蛋白改性聚氨酯型造纸施胶剂及其制备方法。The invention relates to the field of polyurethane application, in particular to a waste skin collagen modified polyurethane type papermaking sizing agent and a preparation method thereof.
背景技术Background technique
聚氨酯型表面施胶剂是最近几年开发的新型表面施胶剂，将其用于表面施胶，可增强纸张的力学性能、抗掉毛、、耐磨性、柔韧性等性能。而单一的水性聚氨酯价格昂贵，而且应用效果受很多因素影响，需要对其进行改性。Polyurethane surface sizing agent is a new type of surface sizing agent developed in recent years. It is used for surface sizing, which can enhance the mechanical properties, anti-lint resistance, wear resistance, flexibility and other properties of paper. However, a single water-based polyurethane is expensive, and the application effect is affected by many factors, so it needs to be modified.
胶原蛋白主要存在于动物的皮肤、软骨、韧带及结缔组织中，来源广泛，而且具有独特的生物活性。我国制革工业中产生大量废弃皮革，如果对其中的胶原蛋白进行提取，利用其活性基团与聚氨酯反应，制备一种新型造纸施胶剂。一方面可降低成本，另一方面可减少环境污染，增加经济效益。Collagen mainly exists in the skin, cartilage, ligament and connective tissue of animals. It has a wide range of sources and has unique biological activity. A large amount of waste leather is produced in my country's tanning industry. If the collagen protein is extracted and its active group is used to react with polyurethane, a new type of paper-making sizing agent is prepared. On the one hand, it can reduce costs, on the other hand, it can reduce environmental pollution and increase economic benefits.
发明内容Contents of the invention
本发明一种废皮胶原蛋白改性聚氨酯型造纸施胶剂及其制备方法，目的在于提供一种低成本、环保型造纸施胶剂的制备方法，该方法利用从废弃皮中提取的胶原蛋白，对聚氨酯进行改性，以期得到一种廉价、高效的造纸助剂。The invention discloses a waste skin collagen modified polyurethane type papermaking sizing agent and a preparation method thereof, the purpose of which is to provide a low-cost, environment-friendly preparation method of a papermaking sizing agent, which utilizes collagen extracted from waste skins , to modify polyurethane in order to obtain a cheap and efficient papermaking auxiliary.
为实现上述目的，本发明采用的技术方案是：In order to achieve the above object, the technical scheme adopted in the present invention is:
一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法，包括以下步骤：A preparation method of waste skin collagen modified polyurethane type papermaking sizing agent, comprising the following steps:
(1)预聚体的制备：异氰酸酯与多元醇化合物在50～70℃下充分反应，制得聚氨酯预聚体；其中，异氰酸酯与多元醇化合物加入量满足-NCO/-OH摩尔比为1.5:1～2:1，反应催化剂为二月桂酸二丁基锡(DBTDL)；(1) Preparation of prepolymer: Isocyanate and polyol compound are fully reacted at 50-70°C to prepare polyurethane prepolymer; wherein, the addition of isocyanate and polyol compound satisfies the -NCO/-OH molar ratio of 1.5: 1～2:1, the reaction catalyst is dibutyltin dilaurate (DBTDL);
(2)预聚体的扩链：向步骤(1)得到的产物中加入亲水扩链剂，50～70℃下反应4～5h后加入胶原蛋白和50-70mL丙酮，充分反应2～3h后，得到淡黄色透明产物；其中，亲水扩链剂与多元醇化合物-OH摩尔比为0.1:1～0.5:1，胶原蛋白质量占反应体系总质量的20％～50％；(2) Chain extension of prepolymer: add hydrophilic chain extender to the product obtained in step (1), react at 50-70°C for 4-5 hours, add collagen and 50-70mL acetone, and fully react for 2-3 hours Finally, a light yellow transparent product is obtained; wherein, the molar ratio of the hydrophilic chain extender to the polyol compound -OH is 0.1:1 to 0.5:1, and the collagen protein accounts for 20% to 50% of the total mass of the reaction system;
(3)预聚体的中和：对步骤(2)得到的产物，进行降温至40℃，加入中和剂进行中和，搅拌混合均匀；(3) Neutralization of the prepolymer: cooling the product obtained in step (2) to 40°C, adding a neutralizing agent for neutralization, stirring and mixing evenly;
(4)乳化：在高速剪切作用力下向步骤(3)产物中加入蒸馏水进行乳化，制得废皮胶原蛋白改性聚氨酯型造纸施胶剂乳液。(4) Emulsification: adding distilled water to the product of step (3) under high-speed shearing force for emulsification to obtain waste hide collagen modified polyurethane type papermaking sizing agent emulsion.
所述步骤2)中胶原蛋白从废弃皮革屑中提取的。The collagen is extracted from waste leather shavings in the step 2).
所述步骤(4)制得废皮胶原蛋白改性聚氨酯型造纸施胶剂乳液后，还包括减压蒸馏去丙酮步骤。The step (4) further includes the step of removing acetone by distillation under reduced pressure after preparing the waste skin collagen modified polyurethane papermaking sizing agent emulsion.
所述步骤(1)中，异氰酸酯化合物为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、异氟尔酮二异氰酸酯(IPDI)中的一种。In the step (1), the isocyanate compound is one of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and isophorone diisocyanate (IPDI).
所述多元醇化合物为聚环氧丙烷二醇(PPG)、聚四氢呋喃(PTMEG)、聚乙二醇(PEG)中的一种。The polyol compound is one of polypropylene oxide glycol (PPG), polytetrahydrofuran (PTMEG), and polyethylene glycol (PEG).
所述亲水扩链剂为酒石酸、二羟甲基丙酸(DMPA)中的一种。The hydrophilic chain extender is one of tartaric acid and dimethylolpropionic acid (DMPA).
所述步骤(4)中，乳化转速为1300r/min，蒸馏水200～300mL，乳化时间30～40min。In the step (4), the emulsification rotation speed is 1300r/min, the distilled water is 200-300mL, and the emulsification time is 30-40min.
所述步骤(3)中中和剂为三乙胺、氨水或氢氧化钠。The neutralizing agent in the step (3) is triethylamine, ammonia or sodium hydroxide.
所述步骤(3)中的中和度为70％～100％。The degree of neutralization in the step (3) is 70% to 100%.
一种废皮胶原蛋白改性聚氨酯型造纸施胶剂，由以上任意一项所述的一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法制得。A waste skin collagen modified polyurethane paper-making sizing agent, which is prepared by the preparation method of a waste skin collagen modified polyurethane paper-making sizing agent described in any one of the above.
与现有技术相比，本发明具有如下优点：Compared with prior art, the present invention has following advantage:
本发明一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法，利用胶原蛋白上较多的氨基(-NH2)、羧基(COOH)和亚氨基(-NH-)等基团与聚氨酯合成过程中的-NCO活性基团接枝反应。结合聚氨酯和胶原蛋白各自的性能优点，一方面保留聚氨酯优异的力学性能、耐磨性、柔韧性、附着力和耐老化性等性能，显著增强施胶纸张的力学、抗压、抗水性能；另一方面加入来源广泛的胶原蛋白原材料，降低产品的成本，减少环境污染的同时创造经济效益。本发明工艺流程简单，易操作。丙酮降黏促进了反应的进度，提高了反应速率。The preparation method of a kind of waste skin collagen modified polyurethane type papermaking sizing agent of the present invention utilizes groups such as more amino (-NH 2 ), carboxyl (COOH) and imino (-NH-) on the collagen to combine with Grafting of -NCO reactive groups during polyurethane synthesis. Combining the performance advantages of polyurethane and collagen, on the one hand, it retains the excellent mechanical properties, abrasion resistance, flexibility, adhesion and aging resistance of polyurethane, and significantly enhances the mechanical, compressive and water-resistant properties of sized paper; On the other hand, collagen raw materials from a wide range of sources are added to reduce the cost of the product, reduce environmental pollution and create economic benefits at the same time. The technological process of the invention is simple and easy to operate. Viscosity reduction with acetone promoted the progress of the reaction and increased the reaction rate.
本发明制得的废皮胶原蛋白改性聚氨酯型造纸施胶剂性能优越，由于胶原蛋白属于生物质资源，基于生物质材料改性的化学品具有良好的生物亲和能力，易生物降解，具有优异的环境友好性，应用前景广泛。The waste skin collagen modified polyurethane paper-making sizing agent prepared by the present invention has superior performance. Since collagen belongs to biomass resources, chemicals modified based on biomass materials have good biological affinity and are easy to biodegrade. Excellent environmental friendliness, broad application prospects.
具体实施方式：Detailed ways:
下面结合具体实施例对本发明作进一步详细说明。The present invention will be described in further detail below in conjunction with specific embodiments.
实施例1：Example 1:
一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法，包括以下步骤：A preparation method of waste skin collagen modified polyurethane type papermaking sizing agent, comprising the following steps:
(1)称取0.03molTDI，0.02mol真空干燥的分子量为1000的PPG，滴加1～2滴DBTDL催化剂，60℃反应2h得到预聚体；(1) Weigh 0.03mol TDI, 0.02mol vacuum-dried PPG with a molecular weight of 1000, add 1 to 2 drops of DBTDL catalyst, and react at 60°C for 2 hours to obtain a prepolymer;
(2)向预聚体中加入0.004mol扩链剂酒石酸，50℃反应4h后，加入占反应体系总质量20％的胶原蛋白和50mL丙酮，60℃反应2h；(2) Add 0.004mol chain extender tartaric acid to the prepolymer, react at 50°C for 4h, add collagen and 50mL acetone accounting for 20% of the total mass of the reaction system, and react at 60°C for 2h;
(3)体系降温至40℃，按中和度70％加入三乙胺中和剂，快速搅拌混合；(3) Cool the system to 40°C, add triethylamine neutralizing agent according to the neutralization degree of 70%, and stir and mix quickly;
(4)在1300r/min高速剪切作用下向反应体系加200ml蒸馏水乳化30min，制得一种废皮胶原蛋白改性聚氨酯型造纸施胶剂白色乳液，最后减压蒸去丙酮。(4) Add 200 ml of distilled water to the reaction system to emulsify for 30 min under high-speed shear at 1300 r/min to prepare a white emulsion of waste skin collagen modified polyurethane type papermaking sizing agent, and finally evaporate the acetone under reduced pressure.
实施例2：Example 2:
一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法，包括以下步骤：A preparation method of waste skin collagen modified polyurethane type papermaking sizing agent, comprising the following steps:
(1)称取0.015molMDI，0.01mol真空干燥的分子量为2000的PTMEG，滴加1～2滴DBTDL催化剂，60℃反应2h得到预聚体；(1) Weigh 0.015mol MDI, 0.01mol vacuum-dried PTMEG with a molecular weight of 2000, add 1 to 2 drops of DBTDL catalyst, and react at 60°C for 2 hours to obtain a prepolymer;
(2)向预聚体中加入0.003mol扩链剂DMPA，60℃反应4h后，加入占反应体系总质量30％的胶原蛋白和50mL丙酮，60℃反应2h；(2) Add 0.003mol chain extender DMPA to the prepolymer, react at 60°C for 4h, add collagen and 50mL acetone accounting for 30% of the total mass of the reaction system, and react at 60°C for 2h;
(3)体系降温至40℃，按中和度80％加入氨水中和剂，快速搅拌混合；(3) The system is cooled to 40°C, and the neutralizing agent in ammonia water is added according to the degree of neutralization of 80%, and the mixture is stirred rapidly;
(4)在1300r/min高速剪切作用下向反应体系加220ml蒸馏水乳化30min，制得一种废皮胶原蛋白改性聚氨酯型造纸施胶剂白色乳液，最后减压蒸去丙酮。(4) Add 220 ml of distilled water to the reaction system for emulsification for 30 min under high-speed shearing at 1300 r/min to prepare a white emulsion of waste skin collagen modified polyurethane type papermaking sizing agent, and finally evaporate the acetone under reduced pressure.
实施例3：Example 3:
一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法，包括以下步骤：A preparation method of waste skin collagen modified polyurethane type papermaking sizing agent, comprising the following steps:
(1)称取0.04molIPDI，0.02mol真空干燥的分子量为1000的PEG，滴加1～2滴DBTDL催化剂，60℃反应2h得到预聚体；(1) Weigh 0.04mol IPDI, 0.02mol vacuum-dried PEG with a molecular weight of 1000, add 1 to 2 drops of DBTDL catalyst, and react at 60°C for 2 hours to obtain a prepolymer;
(2)向预聚体中加入0.008mol扩链剂DMPA，50℃反应4h后，加入占反应体系总质量40％的胶原蛋白和70mL丙酮，60℃反应2h；(2) Add 0.008mol chain extender DMPA to the prepolymer, react at 50°C for 4h, add collagen and 70mL acetone accounting for 40% of the total mass of the reaction system, and react at 60°C for 2h;
(3)体系降温至40℃，按中和度90％加入氢氧化钠中和剂，快速搅拌混合；(3) Cool the system to 40°C, add sodium hydroxide neutralizing agent according to the neutralization degree of 90%, and stir and mix rapidly;
(4)在1300r/min高速剪切作用下向反应体系加200ml蒸馏水乳化，制得一种废皮胶原蛋白改性聚氨酯型造纸施胶剂白色乳液，最后减压蒸去丙酮。(4) Add 200ml of distilled water to the reaction system for emulsification under the action of high-speed shearing at 1300r/min to prepare a white emulsion of waste skin collagen modified polyurethane type papermaking sizing agent, and finally evaporate the acetone under reduced pressure.
实施例4：Example 4:
一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法，包括以下步骤：A preparation method of waste skin collagen modified polyurethane type papermaking sizing agent, comprising the following steps:
(1)称取0.04molIPDI，0.02mol真空干燥的分子量为1000的PEG，滴加1～2滴DBTDL催化剂，60℃反应2h得到预聚体；(1) Weigh 0.04mol IPDI, 0.02mol vacuum-dried PEG with a molecular weight of 1000, add 1 to 2 drops of DBTDL catalyst, and react at 60°C for 2 hours to obtain a prepolymer;
(2)向预聚体中加入0.01mol扩链剂酒石酸，50℃反应4h后，加入占反应体系总质量50％的胶原蛋白和70mL丙酮，60℃反应2h；(2) Add 0.01mol chain extender tartaric acid to the prepolymer, react at 50°C for 4h, add collagen and 70mL acetone accounting for 50% of the total mass of the reaction system, and react at 60°C for 2h;
(3)体系降温至40℃，按中和度100％加入三乙胺中和剂，快速搅拌混合；(3) The temperature of the system is lowered to 40°C, and triethylamine neutralizing agent is added according to the neutralization degree of 100%, and the mixture is stirred rapidly;
(4)在1300r/min高速剪切作用下向反应体系加250ml蒸馏水乳化40min，制得一种废皮胶原蛋白改性聚氨酯型造纸施胶剂白色乳液，最后减压蒸去丙酮。(4) Add 250 ml of distilled water to the reaction system for emulsification for 40 min under high-speed shearing at 1300 r/min to prepare a white emulsion of waste skin collagen modified polyurethane type papermaking sizing agent, and finally evaporate the acetone under reduced pressure.
实施例5：Example 5:
一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法，包括以下步骤：A preparation method of waste skin collagen modified polyurethane type papermaking sizing agent, comprising the following steps:
(1)称取0.03molTDI，0.02mol真空干燥的分子量为1000的PPG，滴加1～2滴DBTDL催化剂，60℃反应2h得到预聚体；(1) Weigh 0.03mol TDI, 0.02mol vacuum-dried PPG with a molecular weight of 1000, add 1 to 2 drops of DBTDL catalyst, and react at 60°C for 2 hours to obtain a prepolymer;
(2)向预聚体中加入0.008mol扩链剂DMPA，50℃反应4h后，加入占反应体系总质量20％的胶原蛋白和60mL丙酮，60℃反应2h；(2) Add 0.008mol chain extender DMPA to the prepolymer, react at 50°C for 4h, add collagen and 60mL acetone accounting for 20% of the total mass of the reaction system, and react at 60°C for 2h;
(3)体系降温至40℃，按中和度70％加入三乙胺中和剂，快速搅拌混合；(3) Cool the system to 40°C, add triethylamine neutralizing agent according to the neutralization degree of 70%, and stir and mix quickly;
(4)在1300r/min高速剪切作用下向反应体系加200ml蒸馏水乳化30min，制得一种废皮胶原蛋白改性聚氨酯型造纸施胶剂白色乳液，最后减压蒸去丙酮。(4) Add 200 ml of distilled water to the reaction system to emulsify for 30 min under high-speed shear at 1300 r/min to prepare a white emulsion of waste skin collagen modified polyurethane type papermaking sizing agent, and finally evaporate the acetone under reduced pressure.
实施例6：Embodiment 6:
一种废皮胶原蛋白改性聚氨酯型造纸施胶剂的制备方法，包括以下步骤：A preparation method of waste skin collagen modified polyurethane type papermaking sizing agent, comprising the following steps:
(1)称取0.015molMDI，0.01mol真空干燥的分子量为2000的PTMEG，滴加1～2滴DBTDL催化剂，60℃反应2h得到预聚体；(1) Weigh 0.015mol MDI, 0.01mol vacuum-dried PTMEG with a molecular weight of 2000, add 1 to 2 drops of DBTDL catalyst, and react at 60°C for 2 hours to obtain a prepolymer;
(2)向预聚体中加入0.003mol扩链剂酒石酸，50℃反应4h后，加入占反应体系总质量30％的胶原蛋白和50mL丙酮，60℃反应2h；(2) Add 0.003mol chain extender tartaric acid to the prepolymer, react at 50°C for 4h, add collagen and 50mL acetone accounting for 30% of the total mass of the reaction system, and react at 60°C for 2h;
(3)体系降温至40℃，按中和度80％加入氨水中和剂，快速搅拌混合；(3) The system is cooled to 40°C, and the neutralizing agent in ammonia water is added according to the degree of neutralization of 80%, and the mixture is stirred rapidly;
(4)在1300r/min高速剪切作用下向反应体系加210ml蒸馏水乳化30min，制得一种废皮胶原蛋白改性聚氨酯型造纸施胶剂白色乳液，最后减压蒸去丙酮。(4) Add 210 ml of distilled water to the reaction system to emulsify for 30 min under high-speed shearing at 1300 r/min to prepare a white emulsion of waste skin collagen modified polyurethane type papermaking sizing agent, and finally evaporate the acetone under reduced pressure.
施胶原理分析：当表面施胶剂涂于纸张表面时，一部分表面施胶液渗透在纸张纤维中，填充纸张中的空隙，使纤维之间进行结合，提高纸张的物理机械强度，并阻止水分子的渗透，增强纸张的耐水性；另一部分施胶剂吸附、留着于纸张表面，在干燥过程中，由于纸张施胶温度高于施胶剂的玻璃化温度，施胶剂表现为热塑性，施胶乳液粒子受热在纸张表面重新分布并铺展，羧基、氨基等亲水基向内与纸张纤维通过氢键、静电引力等作用结合，而其疏水基向外排列，发生疏水基配向，从而形成一层连续的疏水性保护膜，赋予了纸张一定的抗水性。施胶纸张抗水性能见表1。Analysis of sizing principle: When the surface sizing agent is applied to the paper surface, a part of the surface sizing liquid penetrates into the paper fibers, fills the gaps in the paper, makes the fibers bond, improves the physical and mechanical strength of the paper, and prevents water Molecular penetration enhances the water resistance of the paper; another part of the sizing agent is adsorbed and retained on the surface of the paper. During the drying process, since the paper sizing temperature is higher than the glass transition temperature of the sizing agent, the sizing agent is thermoplastic. The sizing emulsion particles are redistributed and spread on the surface of the paper when heated, and the hydrophilic groups such as carboxyl and amino groups are combined with the paper fibers inwardly through hydrogen bonds and electrostatic attraction, while the hydrophobic groups are arranged outward, and the hydrophobic groups are aligned, thus forming A continuous hydrophobic protective film that gives the paper some water resistance. The water resistance of the sized paper is shown in Table 1.
表1Table 1
由上表可以得出，本发明制得的废皮胶原蛋白改性聚氨酯型造纸施胶剂提高了纸张的抗水性，可以作为工业用的抗水剂使用。It can be concluded from the above table that the waste hide collagen modified polyurethane type papermaking sizing agent prepared by the present invention improves the water resistance of paper and can be used as an industrial water resistance agent.
Claims (10)
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| CN105038376A (en) * | 2015-07-30 | 2015-11-11 | 陕西科技大学 | Carboxylic acid type carbamate surfactant as well as preparation method and application thereof |
| CN108913003A (en) * | 2018-05-22 | 2018-11-30 | 陕西科技大学 | A kind of new polyurethane and its purposes as wastewater treatment |
| CN110229308A (en) * | 2019-05-20 | 2019-09-13 | 齐鲁工业大学 | A kind of preparation method of waterborne polyurethane modified collagen-base concrete foamer |
| CN110256651A (en) * | 2019-05-20 | 2019-09-20 | 齐鲁工业大学 | A kind of preparation method of collagen-base papermaking function sizing agent |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038376A (en) * | 2015-07-30 | 2015-11-11 | 陕西科技大学 | Carboxylic acid type carbamate surfactant as well as preparation method and application thereof |
| CN105038376B (en) * | 2015-07-30 | 2017-06-20 | 陕西科技大学 | A kind of carboxylic acid type carbamic acid ester surfactant and its preparation method and application |
| CN108913003A (en) * | 2018-05-22 | 2018-11-30 | 陕西科技大学 | A kind of new polyurethane and its purposes as wastewater treatment |
| CN108913003B (en) * | 2018-05-22 | 2020-08-18 | 陕西科技大学 | A kind of polyurethane, preparation method and use thereof in wastewater treatment |
| CN110229308A (en) * | 2019-05-20 | 2019-09-13 | 齐鲁工业大学 | A kind of preparation method of waterborne polyurethane modified collagen-base concrete foamer |
| CN110256651A (en) * | 2019-05-20 | 2019-09-20 | 齐鲁工业大学 | A kind of preparation method of collagen-base papermaking function sizing agent |
| CN110229308B (en) * | 2019-05-20 | 2021-04-06 | 齐鲁工业大学 | Preparation method of waterborne polyurethane modified collagen-based concrete foaming agent |
| CN110256651B (en) * | 2019-05-20 | 2021-08-31 | 齐鲁工业大学 | Preparation method of collagen-based papermaking functional sizing agent |
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