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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- CN104744663A CN104744663A CN201510141684.1A CN201510141684A CN104744663A CN 104744663 A CN104744663 A CN 104744663A CN 201510141684 A CN201510141684 A CN 201510141684A CN 104744663 A CN104744663 A CN 104744663A
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Abstract
The invention discloses a waste leather collagen modified polyurethane papermaking sizing agent and a preparation method thereof. The method for preparing the papermaking surface sizing agent by modifying the polyurethane by using the collagen extracted from the waste leather meal comprises the following steps: (1) preparing a prepolymer: preparing the polyurethane prepolymer from isocyanate and a polyalcohol compound; (2) performing prepolymer chain extension: adding a hydrophilic chain extender in the product, adding the collagen and a proper amount of acetone, and reacting to obtain a faint yellow transparent product; (3) neutralizing the prepolymer: adding a neutralizing agent, rapidly stirring and mixing; and (4) emulsifying: adding a certain amount of distilling water to emulsify to obtain the waste leather collagen modified polyurethane papermaking sizing agent emulsion. A new papermaking sizing agent is developed by modifying the collagen extracted from the waste leather in the polyurethane aqueous emulsion synthesis process. The solid waste is reduced and the corresponding economic benefit is obtained.
Description
Technical field
The present invention relates to urethane Application Areas, be specifically related to collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather and preparation method thereof.
Background technology
Polyurethane-type Surface Size is the novel surface sizing agent of exploitation recent years, use it for top sizing, the mechanical property of paper can be strengthened, resist to fall hair, the performance such as wear resistance, snappiness.And single aqueous polyurethane is expensive, and effect affects by several factors, needs to carry out modification to it.
Collagen protein is mainly present in the skin of animal, cartilage, ligament and reticular tissue, wide material sources, and has unique biological activity.Produce a large amount of discarded leather in China's tanning industry, if extracted collagen protein wherein, utilize its active group and polyurethane reaction, prepare a kind of new paper making glue.Can reduce costs on the one hand, can environmental pollution be reduced on the other hand, increase economic benefit.
Summary of the invention
Collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather of the present invention and preparation method thereof, object is the preparation method providing a kind of low cost, environment protection type paper sizing agent, the method utilizes the collagen protein extracted from discarded skin, modification is carried out to urethane, to obtaining a kind of cheap, efficient paper making additive.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for the collagen-modified polyurethane-type glue used in paper-making of scrap leather, comprises the following steps:
(1) preparation of performed polymer: isocyanic ester and polyol compound fully react at 50 ~ 70 DEG C, obtained base polyurethane prepolymer for use as; Wherein, it is 1.5:1 ~ 2:1 that isocyanic ester and polyol compound add-on meet-NCO/-OH mol ratio, and catalysts is dibutyl tin laurate (DBTDL);
(2) chain extension of performed polymer: add hydrophilic chain extender in the product that step (1) obtains, adds collagen protein and 50-70mL acetone after reacting 4 ~ 5h, after fully reacting 2 ~ 3h, obtain pale yellow transparent product at 50 ~ 70 DEG C; Wherein, hydrophilic chain extender and polyol compound-OH mol ratio are 0.1:1 ~ 0.5:1, and collagen protein quality accounts for 20% ~ 50% of reaction system total mass;
(3) neutralization of performed polymer: the product obtained step (2), carries out being cooled to 40 DEG C, adds neutralizing agent and neutralize, be uniformly mixed;
(4) emulsification: add distilled water in step (3) product and carry out emulsification under high speed shear reactive force, the obtained collagen-modified polyurethane-type paper-making sizing agent emulsion of scrap leather.
Described step 2) in collagen protein to extract from discarded leather bits.
After the obtained collagen-modified polyurethane-type paper-making sizing agent emulsion of scrap leather of described step (4), also comprise underpressure distillation and go acetone step.
In described step (1), isocyanate compound is the one in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isoflurane chalcone diisocyanate (IPDI).
Described polyol compound is the one in polypropylene oxide glycol (PPG), polytetrahydrofuran (PTMEG), polyoxyethylene glycol (PEG).
Described hydrophilic chain extender is the one in tartrate, dimethylol propionic acid (DMPA).
In described step (4), emulsification rotating speed is 1300r/min, distilled water 200 ~ 300mL, emulsification times 30 ~ 40min.
In described step (3), neutralizing agent is triethylamine, ammoniacal liquor or sodium hydroxide.
Degree of neutralization in described step (3) is 70% ~ 100%.
The collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather, is obtained by the preparation method of the collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather described in above any one.
Compared with prior art, tool of the present invention has the following advantages:
The preparation method of the collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather of the present invention, utilizes amino (-NH more on collagen protein
2) ,-NCO active group graft reaction in the group such as carboxyl (COOH) and imino-(-NH-) and urethane building-up process.In conjunction with urethane and collagen protein feature performance benefit separately, retain the performances such as the mechanical property of urethane excellence, wear resistance, snappiness, sticking power and ageing resistance on the one hand, significantly strengthen the mechanics of sized paper, resistance to compression, water repelling property; Add the collagen protein starting material of wide material sources on the other hand, reduce the cost of product, while reducing environmental pollution, create economic benefit.Present invention process flow process is simple, easy to operate.The glutinous progress facilitating reaction falls in acetone, improves speed of reaction.
The scrap leather that the present invention obtains collagen-modified polyurethane-type glue used in paper-making superior performance, because collagen protein belongs to biomass resource, the chemical based on modified by biomass materials has good biocompatible ability, readily biodegradable, have excellent environment friendly, application prospect is extensive.
Embodiment:
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1:
A preparation method for the collagen-modified polyurethane-type glue used in paper-making of scrap leather, comprises the following steps:
(1) take 0.03molTDI, the vacuum drying molecular weight of 0.02mol is the PPG of 1000, drips 1
~2 DBTDL catalyzer, 60 DEG C of reaction 2h obtain performed polymer;
(2) in performed polymer, add 0.004mol chainextender tartrate, after 50 DEG C of reaction 4h, add the collagen protein and 50mL acetone that account for reaction system total mass 20%, 60 DEG C of reaction 2h;
(3) system is cooled to 40 DEG C, adds triethylamine neutralizing agent by degree of neutralization 70%, and rapid stirring mixes;
(4) 200ml distilled water emulsification 30min is added in 1300r/min high speed shear effect downhill reaction system, obtained a kind of scrap leather collagen-modified polyurethane-type glue used in paper-making white emulsion, last pressure reducing and steaming acetone.
Embodiment 2:
A preparation method for the collagen-modified polyurethane-type glue used in paper-making of scrap leather, comprises the following steps:
(1) take 0.015molMDI, the vacuum drying molecular weight of 0.01mol is the PTMEG of 2000, drips 1
~2 DBTDL catalyzer, 60 DEG C of reaction 2h obtain performed polymer;
(2) in performed polymer, add 0.003mol chainextender DMPA, after 60 DEG C of reaction 4h, add the collagen protein and 50mL acetone that account for reaction system total mass 30%, 60 DEG C of reaction 2h;
(3) system is cooled to 40 DEG C, adds ammonia neutralization agent by degree of neutralization 80%, and rapid stirring mixes;
(4) 220ml distilled water emulsification 30min is added in 1300r/min high speed shear effect downhill reaction system, obtained a kind of scrap leather collagen-modified polyurethane-type glue used in paper-making white emulsion, last pressure reducing and steaming acetone.
Embodiment 3:
A preparation method for the collagen-modified polyurethane-type glue used in paper-making of scrap leather, comprises the following steps:
(1) take 0.04molIPDI, the vacuum drying molecular weight of 0.02mol is the PEG of 1000, drips 1
~2 DBTDL catalyzer, 60 DEG C of reaction 2h obtain performed polymer;
(2) in performed polymer, add 0.008mol chainextender DMPA, after 50 DEG C of reaction 4h, add the collagen protein and 70mL acetone that account for reaction system total mass 40%, 60 DEG C of reaction 2h;
(3) system is cooled to 40 DEG C, adds sodium hydroxide neutralizing agent by degree of neutralization 90%, and rapid stirring mixes;
(4) emulsification of 200ml distilled water is added in 1300r/min high speed shear effect downhill reaction system, obtained a kind of scrap leather collagen-modified polyurethane-type glue used in paper-making white emulsion, last pressure reducing and steaming acetone.
Embodiment 4:
A preparation method for the collagen-modified polyurethane-type glue used in paper-making of scrap leather, comprises the following steps:
(1) take 0.04molIPDI, the vacuum drying molecular weight of 0.02mol is the PEG of 1000, drips 1
~2 DBTDL catalyzer, 60 DEG C of reaction 2h obtain performed polymer;
(2) in performed polymer, add 0.01mol chainextender tartrate, after 50 DEG C of reaction 4h, add the collagen protein and 70mL acetone that account for reaction system total mass 50%, 60 DEG C of reaction 2h;
(3) system is cooled to 40 DEG C, adds triethylamine neutralizing agent by degree of neutralization 100%, and rapid stirring mixes;
(4) 250ml distilled water emulsification 40min is added in 1300r/min high speed shear effect downhill reaction system, obtained a kind of scrap leather collagen-modified polyurethane-type glue used in paper-making white emulsion, last pressure reducing and steaming acetone.
Embodiment 5:
A preparation method for the collagen-modified polyurethane-type glue used in paper-making of scrap leather, comprises the following steps:
(1) take 0.03molTDI, the vacuum drying molecular weight of 0.02mol is the PPG of 1000, drips 1
~2 DBTDL catalyzer, 60 DEG C of reaction 2h obtain performed polymer;
(2) in performed polymer, add 0.008mol chainextender DMPA, after 50 DEG C of reaction 4h, add the collagen protein and 60mL acetone that account for reaction system total mass 20%, 60 DEG C of reaction 2h;
(3) system is cooled to 40 DEG C, adds triethylamine neutralizing agent by degree of neutralization 70%, and rapid stirring mixes;
(4) 200ml distilled water emulsification 30min is added in 1300r/min high speed shear effect downhill reaction system, obtained a kind of scrap leather collagen-modified polyurethane-type glue used in paper-making white emulsion, last pressure reducing and steaming acetone.
Embodiment 6:
A preparation method for the collagen-modified polyurethane-type glue used in paper-making of scrap leather, comprises the following steps:
(1) take 0.015molMDI, the vacuum drying molecular weight of 0.01mol is the PTMEG of 2000, drips 1
~2 DBTDL catalyzer, 60 DEG C of reaction 2h obtain performed polymer;
(2) in performed polymer, add 0.003mol chainextender tartrate, after 50 DEG C of reaction 4h, add the collagen protein and 50mL acetone that account for reaction system total mass 30%, 60 DEG C of reaction 2h;
(3) system is cooled to 40 DEG C, adds ammonia neutralization agent by degree of neutralization 80%, and rapid stirring mixes;
(4) 210ml distilled water emulsification 30min is added in 1300r/min high speed shear effect downhill reaction system, obtained a kind of scrap leather collagen-modified polyurethane-type glue used in paper-making white emulsion, last pressure reducing and steaming acetone.
Principle of neutral sizing is analyzed: when Surface Size is applied to paper surface, and a part of surface size infiltration, in paper fibre, fills the space in paper, make to combine between fiber, improve the physical mechanical strength of paper, and stop the infiltration of water molecules, strengthen the water tolerance of paper; Another part sizing agent adsorbs, keeps in paper surface; in drying process; because paper sizing temperature is higher than the second-order transition temperature of sizing agent; sizing agent shows as thermoplasticity, and sizing emulsions particle is heated and redistributes at paper surface and to sprawl, and the hydrophilic group such as carboxyl, amino inwardly passes through hydrogen bond, electrostatic attraction etc. and acts on and combining with paper fibre; and its hydrophobic group outwards arranges; there is hydrophobic group orientation, thus form one deck continuous print hydrophobicity protective membrane, impart the water resisting property that paper is certain.Sized paper water repelling property is in table 1.
Table 1
Can be drawn by upper table, the collagen-modified polyurethane-type glue used in paper-making of the scrap leather that the present invention obtains improves the water resisting property of paper, can use as industrial water repellent agent.
Claims (10)
1. a preparation method for the collagen-modified polyurethane-type glue used in paper-making of scrap leather, is characterized in that, comprise the following steps:
(1) preparation of performed polymer: isocyanic ester and polyol compound fully react at 50 ~ 70 DEG C, obtained base polyurethane prepolymer for use as; Wherein, it is 1.5:1 ~ 2:1 that isocyanic ester and polyol compound add-on meet-NCO/-OH mol ratio, and catalysts is dibutyl tin laurate;
(2) chain extension of performed polymer: add hydrophilic chain extender in the product that step (1) obtains, adds collagen protein and 50 ~ 70mL acetone after reacting 4 ~ 5h, after fully reacting 2 ~ 3h, obtain pale yellow transparent product at 50 ~ 70 DEG C; Wherein, hydrophilic chain extender and polyol compound-OH mol ratio are 0.1:1 ~ 0.5:1, and collagen protein quality accounts for 20% ~ 50% of reaction system total mass;
(3) neutralization of performed polymer: the product obtained step (2), carries out being cooled to 40 DEG C, adds neutralizing agent and neutralize, be uniformly mixed;
(4) emulsification: add distilled water in step (3) product and carry out emulsification under high speed shear reactive force, the obtained collagen-modified polyurethane-type paper-making sizing agent emulsion of scrap leather.
2. the preparation method of the collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather according to claim 1, is characterized in that: described step 2) in the industrial goods that extract in discarded leather bits of collagen sources.
3. the preparation method of the collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather according to claim 1, it is characterized in that: after the obtained collagen-modified polyurethane-type paper-making sizing agent emulsion of scrap leather of described step (4), also comprise underpressure distillation and go acetone step.
4. the preparation method of the collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather according to claim 1, it is characterized in that: in described step (1), isocyanate compound is tolylene diisocyanate, diphenylmethanediisocyanate or isoflurane chalcone diisocyanate.
5. the preparation method of the collagen-modified polyurethane-type glue used in paper-making of described a kind of scrap leather according to claim 1, is characterized in that: described polyol compound is polypropylene oxide glycol, polytetrahydrofuran or polyoxyethylene glycol.
6. the preparation method of the collagen-modified polyurethane-type glue used in paper-making of described a kind of scrap leather according to claim 1, is characterized in that: described hydrophilic chain extender is tartrate or dimethylol propionic acid.
7. the preparation method of the collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather according to claim 1, it is characterized in that: in described step (4), emulsification rotating speed is 1300r/min, distilled water 200 ~ 300mL, emulsification times 30 ~ 40min.
8. the preparation method of the collagen-modified polyurethane-type glue used in paper-making of described a kind of scrap leather according to claim 1, is characterized in that: the neutralizing agent of described step (3) is triethylamine, ammoniacal liquor or sodium hydroxide.
9. the preparation method of the collagen-modified polyurethane-type glue used in paper-making of described a kind of scrap leather according to claim 1, is characterized in that: the degree of neutralization in described step (3) is 70% ~ 100%.
10. the collagen-modified polyurethane-type glue used in paper-making of scrap leather, is characterized in that: obtained by the preparation method of the collagen-modified polyurethane-type glue used in paper-making of a kind of scrap leather in claim 1 to 9 described in any one.
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| CN201510141684.1A CN104744663A (en) | 2015-03-27 | 2015-03-27 | Waste leather collagen modified polyurethane papermaking sizing agent and preparation method thereof |
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Cited By (4)
| 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 |
| 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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- 2015-03-27 CN CN201510141684.1A patent/CN104744663A/en active Pending
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| 刘堃: "胶原蛋白改性聚氨酯皮革涂饰剂的研制", 《中国优秀博硕士论文全数据库（硕士）工程科技Ι辑》 * |
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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 | Polyurethane, preparation method and application 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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Application publication date: 20150701 |