CN110256651A - A kind of preparation method of collagen-base papermaking function sizing agent - Google Patents

Abstract

The invention discloses a preparation method of a collagen-based papermaking functional sizing agent, which is prepared by using the following components: diisocyanate, polyol, small molecule diol chain extender, hydrophilic chain extender, hydroxypropionate, Neutralizer, hydrolyzed collagen solution, vinyl silane coupling agent, persulfate, water-based resin preservative. The method comprises the following steps: a weighing step, a vinylation modified collagen hydrolyzate step, a polyurethane prepolymer preparation step, a chain extension reaction step, a vinylation sealing step, a neutralization and emulsification step, and a radical copolymerization step. The present invention has the following technical effects: the present invention adopts non-solvated water-based polyurethane to modify collagen, which has the significance of environmental protection; the present invention uses the hydrolyzed protein produced in the tanning production process as raw material to prepare papermaking Functional sizing agent, which greatly solves the problem of high cost of single polyurethane.

Description

Preparation method of a collagen-based papermaking functional sizing agent

technical field

The invention relates to a preparation method of a collagen-based papermaking functional sizing agent, which belongs to the field of fine chemicals.

Background technique

As the world's largest leather producer, China produces millions of tons of chrome-containing leather waste every year. The abandonment of these wastes is a great waste of resources, and it also brings harm to the leather industry and the environment. Enormous pressure. Therefore, how to effectively utilize these wastes is an urgent problem to be solved. There have been a lot of reports on the recycling and reuse of chrome-containing scrap waste, but they are mainly used in leather filling materials, wood adhesives, and concrete foaming agents.

Sizing agent is the most widely used additive in the paper industry. It is used to improve the physical and mechanical strength, printing and dyeing, water resistance and oil resistance of paper. Sizing agents are mainly divided into internal sizing and surface sizing. In-pulp sizing refers to adding a sizing agent during fiber beating, and then making paper, which is used to increase the mechanical strength, water repellency, and folding resistance of paper. Surface sizing refers to coating sizing directly on the surface of paper to increase the water resistance, printing and dyeing and physical and mechanical properties of the paper by forming a functional coating film on the surface of the paper.

At present, the common types of sizing agents mainly include natural polymer materials such as modified starch and modified cellulose, and polymer synthetic materials such as polyvinyl alcohol, styrene-butadiene resin, and water-based polyurethane. The hydrolyzed collagen solution obtained by hydrolysis of chromium-containing scraps by alkali/acid/enzyme method is a high molecular biomaterial with good biodegradability and compatibility. The results of characterization test show that this type of collagen hydrolyzate is a good biomass resource with low manufacturing cost and wide sources, and it also has good viscosity, chelating property and certain film-forming properties.

The invention patent with the patent application number CN201510039181.3 discloses a preparation method of a waste leather industrial gelatin hydrolyzed collagen-based paper-making sizing agent. The collagen hydrolyzate after industrial gelatinase hydrolysis is used as the raw material. Content, heavy metal content and other requirements, in order to reduce the impact on the enzymatic hydrolysis activity. In addition, the current market price of industrial gelatin is 8,000-15,000 yuan/ton, and the cost of raw materials is relatively high.

At the same time, published patents use a large amount of oily acrylic monomers (acrylate, styrene and alkyl methacrylate, etc.) There are a large number of self-polymers formed by acrylic acid oily monomers, and the graft copolymerization rate with collagen polypeptide molecular chains is low, the degree of copolymerization is poor, the degree of phase separation is high, the film-forming quality is brittle, and the water resistance and mechanical strength are poor. Industrialization is difficult higher.

Contents of the invention

The technical problem to be solved by the present invention is to provide a preparation method of collagen-based papermaking functional sizing agent, which increases the way for the recycling of chrome leather waste, and reduces the In order to meet the pressure of the environment, the cost of raw materials used in this method is low, and the requirements for raw material composition indicators are low;

The structure and performance of the sizing agent prepared by the method of the present invention are controllable, and have excellent chelating properties, film-forming properties and structural properties;

The sizing agent prepared by the method of the present invention is applied to the pulp sizing process of papermaking, which effectively improves the dry/wet state mechanical strength, water resistance and folding resistance of the paper, and at the same time retains the calcium carbonate filler has a significant improvement;

The sizing agent prepared by the method of the invention is applied to the surface sizing aid, which can effectively reduce the cracking of the oxidized starch coating film and improve the mechanical strength and water resistance of the paper.

The present invention adopts the following technical scheme, a preparation method of collagen-based papermaking functional sizing agent, which is characterized in that the following components are used to prepare: diisocyanate, polyol, small molecule diol chain extender, hydrophilic chain extender agent, hydroxypropionate, neutralizer, hydrolyzed collagen solution, vinyl silane coupling agent, persulfate, water-based resin preservative.

further improvement

Include the following steps:

1) Weighing step: Weigh the following components in parts by weight: diisocyanate, polyol, small molecule diol chain extender, hydrophilic chain extender, hydroxypropionate, neutralizer, hydrolyzed collagen solution , vinyl silane coupling agent, persulfate, water-based resin preservative;

2) Vinyl modified collagen hydrolyzate step: adjust the pH of the hydrolyzed collagen solution to 4.0-4.5, add vinyl silane coupling agent dropwise, react, and set aside;

3) Polyurethane prepolymer preparation steps: dewater the quantitative polyol in vacuum, lower the temperature, add diisocyanate in the reaction kettle, react, then heat up and keep warm;

4) Chain extension reaction step: cool down the product in step 3), add a hydrophilic chain extender, react, then add a small molecule diol chain extender to the system for chain extension, react, heat up, and keep warm;

5) Vinyl sealing step: cool down the product in step 4), add hydroxypropionate, and react;

6) Neutralization and emulsification: Cool the product in step 5) to room temperature, add a neutralizing agent, neutralize the reaction, add deionized water to stir and emulsify at a high speed, reduce the stirring speed, and continue stirring to obtain a water-based polyurethane prepolymer emulsion;

7) Free radical copolymerization: add the product in step 2) to the water-based polyurethane prepolymer emulsion in step 6), stir evenly, raise the temperature, drop a quantitative persulfate aqueous solution to carry out free radical polymerization, keep warm, cool down, and add water-based resin Preservatives, out of the kettle, the collagen-based functional sizing agent for papermaking is obtained.

further improvement

The hydrolyzed collagen solution in step 2) comes from alkali or acid hydrolyzate of chrome-containing scrap waste, its relative molecular mass is 5000-15000 Da, the solution contains 30%-45% glue, and the viscosity is 100% ~1000 mPa s;

The vinylsilane coupling agent in step 2) is one of vinyltrimethoxysilane, vinyltriethoxysilane or vinyltris(β-methoxyethoxy)silane.

further improvement

The isocyanate in the step 3) is one of toluene diisocyanate or diphenylmethane diisocyanate or isophorone diisocyanate or dicyclohexylmethane diisocyanate;

The polyol is polyether or polyester polyol;

The polyether polyol is one of polyoxypropylene ether diol or polytetrahydrofuran ether diol;

The polyester polyol is one of polybutylene adipate diol or polyethylene adipate diol.

further improvement

When the isocyanate is isophorone diisocyanate or dicyclohexylmethane diisocyanate, 0.1-0.2 part of catalyst is added, and the catalyst is dibutyltin dilaurate or stannous octoate.

further improvement

The small molecule glycol chain extender in step 4) is one of ethylene glycol or propylene glycol or 1,4-butanediol or diethylene glycol;

The hydrophilic chain extender is one of dimethylol propionic acid or dimethylol butyric acid.

further improvement

The hydroxypropionate in step 5) is one of hydroxyethyl methacrylate, hydroxypropyl methacrylate or 4-hydroxybutyl acrylate;

The step 6) neutralizing agent is one of triethylamine or tri-n-butylamine.

further improvement

The initiator in the step 7) is one of sodium persulfate, potassium persulfate or ammonium persulfate; the water-based resin preservative is 5-chloro-2-methyl-4-isothiazolin-3-one or One or more complex products of 2-methyl-4-isothiazolin-3-one or 1,2-benzisothiazolin-3-one.

further improvement

The high-speed stirring speed in step 6) is 1000-1300 r/min, and the stirring speed is reduced to 150-200 r/min.

further improvement

The above-mentioned sizing agents are mainly used in pulp sizing and surface sizing processes in the papermaking process.

The present invention has the following technical effects:

1) The present invention uses solvent-free water-based polyurethane to modify collagen, which has environmental protection significance.

2) The present invention utilizes the hydrolyzed protein of chrome-containing scrap waste produced in the tanning production process as a raw material to prepare papermaking functional sizing agent, which greatly solves the problem of high cost of single polyurethane, and is more easily accepted by the industry; The market price of water-based polyurethane filler is 20,000 to 30,000 yuan/ton, and the cost price of the product of the present invention is 6,000 to 8,000 yuan/ton.

3) The sizing agent prepared by the method of the present invention has good amphoteric charge properties and complexing properties, excellent film-forming properties, water resistance and mechanical strength; its isoelectric point is pH 4~5, and the film resistance The tensile strength is 22~28 MPa, and the surface contact angle is 102.5°.

4) Apply the collagen-based papermaking functional sizing agent of the present invention to the pulp sizing process (addition amount is 1.0% of fiber weight), endow paper with good dry/wet mechanical strength (tensile strength increased by about 20%, tear Crack strength increased by about 12%), water resistance (Cobb value decreased by 18%~20%), folding resistance, printing and dyeing and other properties, and the retention rate of calcium carbonate filler increased to about 35%;

Applied in the surface sizing process (addition amount is 2% of the amount of oxidized starch sizing agent), it will effectively improve the mechanical strength of the paper (the tensile strength is increased by about 12%, the tear strength is increased by 25%~30%), and the resistance Water and folding resistance.

5) The present invention uses the industrial protein produced from the chrome-containing scrap waste produced in the tanning process as a raw material by alkali or acid hydrolyzate, which increases the way for the recycling of chrome leather waste and brings corresponding benefits. At the same time of economic benefits, the pressure on the environment is reduced to a certain extent; through the copolymerization modification with vinyl-blocked waterborne polyurethane, the composite material is endowed with good wettability, chelating property, film-forming property and structural performance.

6) Effectively improve the shortcomings of single collagen hydrolyzate as a paper-making filler, such as low retention rate, poor film-forming property, and poor structural strength;

A large number of electron-rich groups (-NH ₂ , -COO ^- , -OH, etc.) in the molecular structure of the sizing agent of the present invention play the role of complexing calcium carbonate, which will greatly improve the retention rate of calcium carbonate; in addition, the present invention The good film-forming properties of the invented sizing agent and the good mechanical properties of the film, as well as the water and solvent resistance properties, applied to the surface sizing of paper and adding additives, will greatly reduce the cracking of the oxidized starch coating film on the paper and improve the final paper mechanical strength and water resistance.

7) The present invention utilizes the flexible and controllable structural design of water-based polyurethane, excellent film-forming properties, water resistance, structural strength, and good affinity with cellulose, and through the copolymerization modification of vinyl-enclosed water-based polyurethane, Then carry out controllable aqueous phase emulsion free radical copolymerization with vinyl silane coupling agent modified collagen hydrolyzate to obtain an environmentally friendly water-based polyurethane modification with controllable structure and performance, excellent chelating properties, film-forming properties and structural properties. Collagen-based functional sizing agent for papermaking.

8) Adopting the method of the present invention to prepare the sizing agent greatly reduces the cost of raw materials (the current market price of industrial gelatin is 8,000-15,000 yuan/ton, and the current market price of the industrial protein of this patent is 5,000-7,000 yuan/ton) and the effect on protein Raw material index requirements.

Description of drawings

Fig. 1 is a preparation process flow chart of the present invention;

Fig. 2 is that sizing agent of the present invention is used for calcium carbonate retention application effect diagram when sizing in slurry;

Fig. 3 is an application effect diagram of the surface sizing of the sizing agent of the present invention.

Detailed ways

Embodiment 1, a preparation method of a collagen-based papermaking functional sizing agent, adopts a stainless steel anti-exposure reaction kettle, has a vacuum dewatering, heating and cooling, condensation reflux, constant pressure dripping device, comprising the following steps:

(1) Put 300 kg of 40% hydrolyzed collagen solution into a 1 t stainless steel explosion-proof reaction kettle, add about 12 kg of 15% HCl, stir evenly, until the pH of the reaction solution reaches 3.0-3.5, add 5 kg of vinyltrimethoxysilane dropwise , about 1 hour after dripping, react at 50°C for 60 minutes to obtain pre-modified hydrolyzed collagen solution, set aside;

(2) Weigh 50 kg of polyoxypropylene ether diol (molecular weight 2000), vacuum dehydrate at 110°C for 1~2 h, cool down to 60°C, add 25 kg of toluene diisocyanate to react for 1 h, heat up to 82°C, Incubate for 1 h to obtain prepolymer;

(3) Add 3 kg of dimethylolpropionic acid to the prepolymer in (2) for chain extension, react at 60°C for 1 h, add 5 kg of 1,4-butanediol for chain extension, and react at 60°C Insulate for 1 h, heat up to 80°C, and react for 2-3 h;

(4) Add 5.5 kg of hydroxyethyl methacrylate to (3) for vinylation, and react at 65°C for 1~2 h until no -NCO is detected.

(5) Cool down to 50°C, add 2.2 kg of triethylamine for neutralization, and the reaction time is 15-20 min. After cooling down to room temperature, add 5°C deionized water at 1200 r/min and stir for 5 min to obtain vinylated water-based polyurethane prepolymer emulsion;

(6) Add (1) pre-modified hydrolyzed collagen solution into (5) water-based polyurethane prepolymer emulsion under high-speed shear at 500 r/min, stir at room temperature for 10 min, then reduce the stirring speed to 150-200 r/min. Raise the temperature to 82~84°C, add potassium persulfate solution dropwise to initiate polymerization by free radicals, finish dripping in 30~60 minutes, continue to keep warm for 30~40 minutes, cool down to below 45°C, add 0.5 kg 5-chloro-2- Methyl-4-isothiazolin-3-one (content about 15%) is taken out of the kettle to obtain collagen-based functional sizing agent for papermaking.

Embodiment 2, a kind of preparation method of collagen-based papermaking functional sizing agent, comprises the following steps:

(1) Put 300 kg of 40% hydrolyzed collagen solution into a 1 t stainless steel explosion-proof reaction kettle, add about 12 kg of 15% HCl, stir evenly, until the pH of the reaction solution reaches 3.0-3.5, add 5.5 kg of vinyltriethoxy Silane, about 1 hour to drop, react at 50°C for 60 minutes to obtain pre-modified hydrolyzed collagen solution, set aside;

(2) Weigh 50 kg of polytetrahydrofuran ether diol (molecular weight 2000), vacuum dehydrate at 110°C for 1~2 h, cool down to 60°C, add 30 kg of isophorone diisocyanate, 0.1 kg of dibutyltin dilaurate Catalyst, reaction 1 h, be warming up to 82 ℃, insulation 1 h obtains prepolymer;

(3) Add 3.5 kg of dimethylolbutyric acid to the prepolymer in (2) for chain extension, react at 60°C for 1 h, add 4 kg of propylene glycol to the system for chain extension, keep at 60°C for 1 h, Warming up to 80°C, reacting for 3-4 h;

(4) Add 5 kg of hydroxypropyl methacrylate to (3) for vinylation, and react at 65°C for 1~2 h until no -NCO is detected.

(5) Cool down to 50°C, add 2.4 kg of triethylamine for neutralization, and the reaction time is 15-20 min. After cooling down to room temperature, add 5°C deionized water at 1200 r/min and stir for 5 min to obtain vinylated water-based polyurethane prepolymer emulsion;

(6) Add (1) pre-modified hydrolyzed collagen solution into (5) water-based polyurethane prepolymer emulsion under high-speed shear at 500 r/min, stir at room temperature for 10 min, then reduce the stirring speed to 150-200 r/min. Raise the temperature to 82~84°C, add ammonium persulfate solution dropwise to initiate polymerization by free radicals, finish dripping in 30~60 minutes, continue to keep warm for 30~40 minutes, cool down to below 45°C, add 0.5 kg 2-methyl-4 -Isothiazolin-3-one water-based resin preservative (active content about 14%~16%), out of the kettle, to obtain collagen-based papermaking functional sizing agent.

Embodiment 3, a kind of preparation method of collagen-based papermaking functional sizing agent, comprises the following steps:

(1) Put 300 kg of 40% hydrolyzed collagen solution into a 1 t stainless steel explosion-proof reaction kettle, add about 12 kg of 15% HCl, stir evenly, until the pH of the reaction solution reaches 3.0-3.5, add 6 kg of vinyl tris(β- Methoxyethoxy) silane, dripped in about 1 hour, and reacted at 50°C for 60 minutes to obtain a pre-modified hydrolyzed collagen solution for later use;

(2) Weigh 38 kg of diphenylmethane diisocyanate and 75 kg of polyoxypropylene ether diol (molecular weight: 3000) after vacuum dehydration, react at 65°C for 1 h, heat up to 82°C, and keep warm for 1-2 h to obtain Prepolymer;

(3) Add 5 kg of dimethylolpropionic acid to the prepolymer in (2) for chain extension, react at 60°C for 1 h, add 5.5 kg of diethylene glycol for chain extension, and keep warm at 60°C for 1 hour h, be warming up to 80 DEG C, react 2～3 h;

(4) Add 5.6 kg of 4-hydroxybutyl acrylate to (3) for vinylation, and react at 65°C for 1~2 h until no -NCO is detected.

(5) Cool down to 50°C, add 6.5 kg of tri-n-butylamine for neutralization, and the reaction time is 15-20 min. After cooling down to room temperature, add 5°C deionized water at 1200 r/min and stir for 5 min to obtain vinylated water-based polyurethane prepolymer emulsion;

(6) Add (1) pre-modified hydrolyzed collagen solution into (5) water-based polyurethane prepolymer emulsion under high-speed shear at 500 r/min, stir at room temperature for 10 min, then reduce the stirring speed to 150-200 r/min. Raise the temperature to 82~84°C, add dropwise sodium persulfate solution to initiate polymerization by free radicals, finish dripping in 30~60 minutes, continue to keep warm for 30~40 minutes, cool down to below 45°C, add 0.5 kg1,2-benzoiso Thiazolin-3-one (active content about 12%~15%) is taken out of the kettle to obtain collagen-based papermaking functional sizing agent.

Embodiment 4 A preparation method of a collagen-based papermaking functional sizing agent, comprising the following steps:

(1) Put 300 kg of 40% hydrolyzed collagen solution into a 1 t stainless steel explosion-proof reaction kettle, add about 12 kg of 15% HCl, stir evenly, until the pH of the reaction solution reaches 3.0-3.5, add 5 kg of vinyltrimethoxysilane dropwise , about 1 hour after dripping, react at 50°C for 60 minutes to obtain pre-modified hydrolyzed collagen solution, set aside;

(2) Weigh 50 kg polybutylene adipate diol (molecular weight: 2000), vacuum dehydrate at 110°C for 1~2 h, cool down to 60°C, add 40 kg dicyclohexylmethane diisocyanate, 0.1 kg Stannous octoate catalyst, reaction 1 h, be warming up to 82 ℃, insulation 1～2 h obtains prepolymer;

(3) Add 4 kg of dihydroxypropionic acid to the prepolymer in (2) for chain extension, react at 60°C for 1 h, add 3.5 kg of ethylene glycol to the system for chain extension, and keep warm at 60°C for 1 h, Warming up to 82°C, reacting for 2 to 3 h;

(4) Add 5.5 kg of hydroxyethyl methacrylate to (3) for vinylation, and react at 65°C for 1~2 h until no -NCO is detected.

(5) Cool down to 50°C, add 3 kg of triethylamine for neutralization, and the reaction time is 15-20 min. After cooling down to room temperature, add 5°C deionized water at 1200 r/min and stir for 5 min to obtain vinylated water-based polyurethane prepolymer emulsion;

(6) Add (1) pre-modified hydrolyzed collagen solution into (5) water-based polyurethane prepolymer emulsion under high-speed shear at 500 r/min, stir at room temperature for 10 min, then reduce the stirring speed to 150-200 r/min. Raise the temperature to 82~84°C, add dropwise sodium persulfate solution to initiate polymerization by free radicals, finish dripping in 30~60 minutes, continue to keep warm for 30~40 minutes, cool down to below 45°C, add 0.5 kg1,2-benzoiso Thiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one compound preservative (active content about 12%~15%), out of the kettle, can obtain collagen-based papermaking function Sizing agent.

Embodiment 5, a kind of preparation method of collagen-based papermaking functional sizing agent, comprises the following steps:

(1) Put 300 kg of 40% hydrolyzed collagen solution into a 1 t stainless steel explosion-proof reaction kettle, add about 12 kg of 15% HCl, stir evenly, until the pH of the reaction solution reaches 3.0-3.5, add 5.5 kg of vinyltriethoxy Silane, about 1 hour to drop, react at 50°C for 60 minutes to obtain pre-modified hydrolyzed collagen solution, set aside;

(2) Weigh 50 kg of polyethylene adipate diol (molecular weight: 2000), vacuum dehydrate at 110°C for 1~2 h, cool down to 60°C, add 25 kg of toluene diisocyanate to react for 1 h, and heat up to 82 DEG C, insulation 1 h obtains prepolymer;

(3) Add 4 kg of dimethylolbutyric acid to the prepolymer in (2) for chain extension, react at 60°C for 1 h, add 5.7 kg of diethylene glycol for chain extension, and keep warm at 60°C for 1 hour h, be warming up to 82 DEG C, react 2～3 h;

(4) Add 5.6 kg of hydroxypropyl methacrylate to (3) for vinylation, and react at 65°C for 1~2 h until no -NCO is detected.

(5) Cool down to 50°C, add 2.7 kg of triethylamine for neutralization, and the reaction time is 15-20 min. After cooling down to room temperature, add 5°C deionized water at 1200 r/min and stir for 5 min to obtain vinylated water-based polyurethane prepolymer emulsion;

(6) Add (1) pre-modified hydrolyzed collagen solution into (5) water-based polyurethane prepolymer emulsion under high-speed shear at 500 r/min, stir at room temperature for 10 min, then reduce the stirring speed to 150-200 r/min. Raise the temperature to 82~84°C, add ammonium persulfate solution dropwise to initiate polymerization by free radicals, finish dripping in 30~60 minutes, continue to keep warm for 30~40 minutes, cool down to below 45°C, add 0.5 kg 2-methyl-4 -Isothiazolin-3-one and 1,2-benzisothiazolin-3-one compound preservative (active content about 14%~16%), out of the kettle, to obtain collagen-based papermaking functional sizing agent .

Example 6, the following examples are used to illustrate that this product is used as a papermaking sizing agent for internal pulp sizing and surface sizing.

In-pulp sizing application: Weigh a certain quality hardwood pulp board for beating, and the beating degree is 40°SR. Weigh a certain amount of slurry, disintegrate and disperse it in a pulp breaker, disperse at a high speed of 2000 r/min for 20 s, and add 1.0% of this patented sizing agent and 25% calcium carbonate filler (based on the weight of dry pulp) meter), and disperse evenly in the pulp breaker. A fast Kaiser method was used to copy the sheets, the vacuum degree was 0.1 MPa, the temperature was 95°C, the drying time was 10 minutes, and the weight of the sheets was 60g/m ² . The tensile strength of the prepared paper is 38.26 MPa, the tear strength is 1.884 MPa, the Cobb value is 140.56, the folding endurance is 8, and the calcium carbonate retention rate is 25.67%. The SEM image of calcium carbonate retention is shown in Figure 2.

Surface sizing application: Mix 2.0% of this patented sizing agent (based on the weight of dry oxidized starch) with 20% gelatinized starch solution and apply it on the surface of the paper. After sizing, bake at 105°C for 10 minutes . Surface sized paper test results: Compared with the blank (without adding the patented sizing agent), the tensile strength increased by about 12%, the tear strength by 25%~30%, the Cobb value decreased by about 20%, and the folding endurance increased by 1 ~3, see Figure 3 The cracking rate of the coating has been effectively reduced.

Claims (10)

1. a kind of preparation method of collagen-base papermaking function sizing agent, which is characterized in that prepared using lower component: two isocyanides Acid esters, polyalcohol, small molecule glycol chain extender, hydrophilic chain extender, hydracrylic acid acid esters, neutralizer, Hydrolyzed Collagen liquid, Vinyl silicane coupling agent, persulfate, water-base resin preservative.

2. the preparation method of collagen-base papermaking function sizing agent according to claim 1, which is characterized in that including with Lower step:

1) it weighs step: weighing following components: diisocyanate, polyalcohol, small molecule glycol chain extender, parent according to parts by weight Water chain extender, hydracrylic acid acid esters, neutralizer, Hydrolyzed Collagen liquid, vinyl silicane coupling agent, persulfate, aqueous tree Rouge preservative；

2) vinylated modified collagen hydrolysate step: Hydrolyzed Collagen liquid is adjusted into pH to 4.0~4.5, vinyl is added dropwise Silane coupling agent, reaction are spare；

3) polyurethane prepolymer preparation step: by quantitative polyalcohol vaccum dewatering, diisocyanate is added in reaction kettle in cooling In, then reaction heats up, keep the temperature；

4) chain extending reaction step: product in step 3) is cooled down, and hydrophilic chain extender is added, then reaction is added small into system Molecule glycol chain extender carries out chain extension, reacts, and heats up, heat preservation；

5) vinylated closing step: product in step 4) is cooled down, and hydracrylic acid acid esters, reaction is added；

6) it neutralizes, emulsify: product in step 5) is cooled to room temperature, neutralizer is added, deionized water high speed is added in neutralization reaction Stirring and emulsifying reduces mixing speed, continues to stir, obtain Waterborne Polyurethane Prepolymer lotion；

7) free-radical polymerized: product in step 2 being added in step 6) Waterborne Polyurethane Prepolymer lotion, is stirred evenly, is risen Temperature is added dropwise quantitative persulfate aqueous solution and carries out free radical polymerization, keeps the temperature, and water-base resin preservative is added, out in cooling Kettle is to get collagen-base papermaking function sizing agent.

3. the preparation method of collagen-base papermaking function sizing agent according to claim 2, which is characterized in that the step It is rapid 2) in Hydrolyzed Collagen liquid is white is from the discarded alkaloids of the particle of skin containing chromium or Acid hydrolysis product, relative molecular mass 5000~15000 Da, solution gel content are the % of 30 %~45, and viscosity is in 100~1000 mPa s；

The step 2 medium vinyl silane coupling agent is vinyltrimethoxysilane or vinyltriethoxysilane or second One of three silane of alkenyl.

4. the preparation method of collagen-base papermaking function sizing agent according to claim 2, which is characterized in that

Isocyanates in the step 3) is that toluene di-isocyanate(TDI) or '-diphenylmethane diisocyanate or isophorone two are different One of cyanate or dicyclohexyl methyl hydride diisocyanate；

Polyalcohol is polyethers or polyester polyol；

Polyether polyol is one of polypropylene oxide ether glycol or polytetrahydrofuran ether glycol；

Polyester polyol is one of polybutylene glyool adipate or polyethylene glycol adipate glycol.

5. the preparation method of collagen-base papermaking function sizing agent according to claim 4, which is characterized in that described different Cyanate is isophorone diisocyanate or dicyclohexyl methyl hydride diisocyanate, and 0.1~0.2 part of catalyst, institute is added Stating catalyst is dibutyl tin dilaurate or stannous octoate.

6. the preparation method of collagen-base papermaking function sizing agent according to claim 2, which is characterized in that the step It is rapid 4) in small molecule glycol chain extender be ethylene glycol or propylene glycol or one of 1,4- butanediol or diglycol；

Hydrophilic chain extender is one of dihydromethyl propionic acid or dimethylolpropionic acid.

7. the preparation method of collagen-base papermaking function sizing agent according to claim 2, which is characterized in that the step It is rapid 5) in hydracrylic acid acid esters be hydroxyethyl methacrylate or hydroxy propyl methacrylate or 4- hydroxybutyl acrylate One of；

The step 6) neutralizer is one of triethylamine or tri-n-butylamine.

8. the preparation method of collagen-base papermaking function sizing agent according to claim 2, which is characterized in that the step It is rapid 7) in initiator be one of sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate；Water-base resin preservative is the chloro- 2- of 5- Methyl -4- isothiazoline -3- ketone or one of 2-methyl-4-isothiazolin-3-one or 1,2- benzisothiazole-3-ketone or Several compounding products.

9. the preparation method of collagen-base papermaking function sizing agent according to claim 2, which is characterized in that step 6) In high-speed stirred revolving speed be 1000 ~ 1300 r/min, reduce mixing speed after revolving speed be 150 ~ 200 r/min.

10. the preparation method of collagen-base papermaking function sizing agent according to claim 2, which is characterized in that above-mentioned Sizing agent is mainly used in plasm-glue-blending and top sizing process in paper-making process.