CN102286204B - Preparation method for synthesizing composite material by using fiber of waste paper and collagen of waste leather - Google Patents

Preparation method for synthesizing composite material by using fiber of waste paper and collagen of waste leather Download PDF

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CN102286204B
CN102286204B CN201110108941A CN201110108941A CN102286204B CN 102286204 B CN102286204 B CN 102286204B CN 201110108941 A CN201110108941 A CN 201110108941A CN 201110108941 A CN201110108941 A CN 201110108941A CN 102286204 B CN102286204 B CN 102286204B
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collagen
waste paper
deinking
paper fibre
mass ratio
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CN102286204A (en
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王立娟
谭银菲
刘彬
李鹏飞
谷明波
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Northeast Forestry University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention discloses a preparation method for synthesizing a composite material by using the fiber of waste paper and the collagen of waste leather and relates to a preparation method of the composite material. The preparation method solves the problem that solid waste generated by cutting and shearing after tanning the leather pollutes the environment to cause loss of collagen protein. The preparation method comprises the following steps of: 1, carrying out deinking treatment on the fiber of the waste paper; and 2, mixing the collagen, water, the deinked fiber of the waste paper and a plasticizer, then dripping a cross-linking agent, simultaneously adjusting the pH value to react, drying, forming and obtaining the composite material. The raw materials used by the invention are waste materials, the wastes are changed into valuables, the problems of environmental pollution and loss of the collagen protein are solved, and the fiber distribution of the waste paper used by the invention is 0.01-0.05mm; and in the composite material prepared by the method, the tensile strength can reach 5.06MPa, the elastic modulus is 0.09GPa and the swelling rate can reach 31.20%.

Description

Preparing method with waste paper fibre and discarded leather collagen synthetic composite material
Technical field
The present invention relates to a kind of preparation method of matrix material.
Background technology
Along with people's is to the attention of environment, and the development and use of environmental friendliness type material progressively become the focus that common people pay close attention to.Utilize the depleted resource to prepare high performance novel material, gradually reduce the consumption of Nonrenewable resources, environment is significant for preserving our planet.
In recent years, because world's paper and cardboard consumption constantly increase, the generation of waste paper also constantly increases.The environmental consciousness of Along with people's constantly strengthens, and waste paper utilizes day by day and comes into one's own.Waste paper is the secondary vegetable fibre of reuse, has the series of advantages of vegetable fibre: cheap, density is little, has higher modulus of elasticity, and is close with inorganic fibre, and its biological degradability and recyclability are the most outstanding advantages.The countries in the world waste paper recovery generally rises at present, and the waste paper recovery of Korea S, Germany has reached 75%.It mainly is used to matrix material, functional materials, wrapping material.Be mainly used in preparation thermoplastic polymer matrix material, cement-base composite material, Biodegradable resin matrix material at field of compound material waste paper, but when other matrix materials of preparation, study lessly relatively.Simultaneously considerable progress has been obtained about the research of waste paper reutilization technology in countries in the world, but product the research aspect the safety is also seldom in environment for use.
China is a tanning industry big country; Traditional tanning industry causes a large amount of losses of Animal resources; Contain 30% protein approximately in the solid waste that cutting and cutting produce after the tanning, China produces more than 140 ten thousand tons of such leather solid waste every year approximately, if contain more than 50 ten thousand tons of cadmium solid waste. can not these solid waste reasonably be handled; Not only can serious environment pollution, and can cause a large amount of losses of collagen protein.Collagen protein is the precious natural resources that can utilize again, also is one of green resource few in number simultaneously.At present, collagen widespread use in fields such as foodstuffs industry, biological medicine, nutritive health-care.But it is poor that collagen has physical and mechanical properties as natural materials, biodegradable, and the general relatively poor characteristics of synthetic materials stable mechanical property but biocompatibility.Therefore, preparation collagen-polymer composite makes its common advantage that has two kinds of materials simultaneously, will have development prospect widely.
According to the characteristics that waste paper fibre and collagen protein self have, these two kinds of materials are carried out the compound higher and degradable composite material of a kind of intensity that is expected to obtain, make it can be able in wrapped pad barrier material field use.The present invention is the feedstock production degradable composite material with two kinds of wastes, has both alleviated environmental stress, has opened up new road for waste utilizes again again.
Summary of the invention
The objective of the invention is provides a kind of preparation method with waste paper fibre and discarded leather collagen synthetic composite material in order to solve the noxious waste pollution environment that cutting and cutting produce after the tanning, the problem that causes the collagen protein loss.
The present invention is following with the preparation method of waste paper fibre and discarded leather collagen synthetic composite material: one, the deinking of waste paper fibre is handled: with NaOH, H 2O 2, Na 2SiO 39H 2O or H 2O and waste paper fibre are according to 1～3.5: 100 mass ratio mixes in the water-bath that is incorporated in 60 ℃～70 ℃ and reacts 1h～1.5h, removes impurity and moisture then, gets the waste paper fibre of deinking; Two, with after collagen and the mixed of water according to 1g: 6mL; Waste paper fibre and collagen mass ratio according to deinking are 10～15: 100, softening agent and collagen mass ratio are waste paper fibre and the softening agent that 10～12.5: 100 ratio adds deinking; In 30 ℃～65 ℃ water-bath, fully stir; Be that 10～15: 100 ratio drips linking agent in linking agent and collagen mass ratio then; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5～9.7; Under 50 ℃～100 ℃ condition, react 0.5h～3h again, and then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material; Linking agent described in the step 2 is LUTARALDEHYDE or N-N ' methylene-bisacrylamide; Described softening agent is USP Kosher or DOP.
The used starting material of the present invention are waste material; Turn waste into wealth and solved the problem of environmental pollution and collagen protein loss; The used waste paper fibre of the present invention is distributed as 0.01mm～0.05mm; Adopt the tensile strength of the matrix material of present method preparation can reach 5.06MPa, Young's modulus 0.09GPa, swelling ratio can reach 31.20%.
Description of drawings
Fig. 1 be not deinking newspaper fibre content (deinking newspaper fiber does not account for the quality percentage composition of collagen) to the influence curve of composite material tensile strength; Fig. 2 be not deinking newspaper fibre content (deinking newspaper fiber does not account for the quality percentage composition of collagen) to the influence curve of matrix material Young's modulus; Fig. 3 be in embodiment eight step 2 pH value to the influence curve of gained composite material tensile strength; Fig. 4 be in embodiment eight step 2 pH value to the influence curve of gained matrix material Young's modulus; Fig. 5 be in the embodiment nine not in deinking newspaper fiber and the embodiment ten deinking newspaper fiber to the influence curve of gained composite material tensile strength; The tensile strength curve of gained matrix material in
Figure BDA0000058230190000021
expression body embodiment nine among the figure, the tensile strength curve of gained matrix material in
Figure BDA0000058230190000022
expression body embodiment ten; Fig. 6 be in the embodiment nine not in deinking newspaper fiber and the embodiment ten deinking newspaper fiber to the influence curve of gained matrix material Young's modulus, the Young's modulus curve of gained matrix material in Young's modulus curve
Figure BDA0000058230190000024
the expression body embodiment ten of gained matrix material in
Figure BDA0000058230190000023
expression body embodiment nine among the figure; Fig. 7 be in the embodiment 11 glutaraldehyde content to the influence curve of gained composite material tensile strength; Fig. 8 be in the embodiment 11 glutaraldehyde content to the influence curve of gained matrix material Young's modulus; Fig. 9 be in the embodiment 12 USP Kosher content to the influence curve of gained composite material tensile strength; Figure 10 be in the embodiment 12 USP Kosher content to the influence curve of gained matrix material Young's modulus; Figure 11 be not deinking chancery paper fibre content (deinking chancery paper fiber does not account for the quality percentage composition of collagen) to the influence curve of composite material tensile strength;
Figure 12 be not deinking chancery paper fibre content (deinking chancery paper fiber does not account for the quality percentage composition of collagen) to the influence curve of matrix material Young's modulus; Figure 13 be in embodiment 13 step 2 pH value to the influence curve of gained composite material tensile strength; Figure 14 be in embodiment 13 step 2 pH value to the influence curve of gained matrix material Young's modulus; Figure 15 be in the embodiment 14 not in deinking chancery paper fiber and the embodiment 15 deinking chancery paper fiber to the influence curve of gained composite material tensile strength; The tensile strength curve of gained matrix material in
Figure BDA0000058230190000031
expression body embodiment 14 among the figure, the tensile strength curve of gained matrix material in expression body embodiment 15; Figure 16 be in the embodiment 14 not in deinking chancery paper fiber and the embodiment 15 deinking chancery paper fiber to the influence curve of gained matrix material Young's modulus; The Young's modulus curve of gained matrix material in
Figure BDA0000058230190000033
expression body embodiment 14 among the figure, the Young's modulus curve of gained matrix material in
Figure BDA0000058230190000034
expression body embodiment 15; Figure 17 be in the embodiment 16 glutaraldehyde content to the influence curve of gained composite material tensile strength; Figure 18 be in the embodiment 16 glutaraldehyde content to the influence curve of gained matrix material Young's modulus; Figure 19 be in the embodiment 17 USP Kosher content to the influence curve of gained composite material tensile strength; Figure 20 be in the embodiment 17 USP Kosher content to the influence curve of gained matrix material Young's modulus; Figure 21 is N in the embodiment 18, the influence curve of N '-methylene-bisacrylamide content gained composite material tensile strength; Figure 22 is N in the embodiment 18, the influence curve of N '-methylene-bisacrylamide content gained matrix material Young's modulus; Figure 23 be in the embodiment 19 two kinds of linking agents to the influence curve of gained composite material tensile strength;
Figure BDA0000058230190000035
expression LUTARALDEHYDE is to the influence curve of gained composite material tensile strength among the figure; representes N, and N '-methylene-bisacrylamide is to the influence curve of gained composite material tensile strength; Figure 24 be in the embodiment 19 among two kinds of linking agent influence curve figure to gained matrix material Young's modulus
Figure BDA0000058230190000037
expression LUTARALDEHYDE to the influence curve of gained matrix material Young's modulus; representes N, and N '-methylene-bisacrylamide is to the influence curve of gained matrix material Young's modulus; Figure 25 be in the embodiment 20 DOP content to the influence curve of gained composite material tensile strength; Figure 26 be in the embodiment 20 DOP content to the influence curve of gained matrix material Young's modulus; Figure 27 be in the embodiment 21 two kinds of softening agent to the influence curve of gained composite material tensile strength;
Figure BDA0000058230190000039
expression USP Kosher is to the influence curve of gained composite material tensile strength among the figure, and
Figure BDA00000582301900000310
expression DOP is to the influence curve of gained composite material tensile strength; Figure 28 is that
Figure BDA00000582301900000311
expression USP Kosher is to the influence curve of gained matrix material Young's modulus among two kinds of softening agent influence curve figure to gained matrix material Young's modulus in the embodiment 21, and
Figure BDA00000582301900000312
expression DOP is to the influence curve of gained matrix material Young's modulus; Figure 29 is N in the embodiment 22, the influence curve of N '-methylene-bisacrylamide content gained composite material tensile strength; Figure 30 is N in the embodiment 22, the influence curve of N '-methylene-bisacrylamide content gained matrix material Young's modulus; Figure 31 be in the embodiment 23 two kinds of linking agents to the influence curve of gained composite material tensile strength;
Figure BDA00000582301900000313
expression LUTARALDEHYDE is to the influence curve of gained composite material tensile strength among the figure;
Figure BDA00000582301900000314
representes N, and N '-methylene-bisacrylamide is to the influence curve of gained composite material tensile strength; Figure 32 be in the embodiment 23 among two kinds of linking agent influence curve figure to gained matrix material Young's modulus
Figure BDA00000582301900000315
expression LUTARALDEHYDE to the influence curve of gained matrix material Young's modulus;
Figure BDA00000582301900000316
representes N, and N '-methylene-bisacrylamide is to the influence curve of gained matrix material Young's modulus; Figure 33 be in the embodiment 24 DOP content to the influence curve of gained composite material tensile strength; Figure 34 be in the embodiment 24 DOP content to the influence curve of gained matrix material Young's modulus; Figure 35 be in the embodiment 25 two kinds of softening agent to the influence curve of gained composite material tensile strength; expression USP Kosher is to the influence curve of gained composite material tensile strength among the figure, and expression DOP is to the influence curve of gained composite material tensile strength; Figure 36 is that
Figure BDA0000058230190000043
expression USP Kosher is to the influence curve of gained matrix material Young's modulus among two kinds of softening agent influence curve figure to gained matrix material Young's modulus in the embodiment 25, and expression DOP is to the influence curve of gained matrix material Young's modulus.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: with NaOH, H 2O 2, Na 2SiO 39H 2O or H 2O and waste paper fibre are according to 1～3.5: 100 mass ratio mixes in the water-bath that is incorporated in 60 ℃～70 ℃ and reacts 1h～1.5h, removes impurity and moisture then, gets the waste paper fibre of deinking; Two, with after collagen and the mixed of water according to 1g: 6mL; Waste paper fibre and collagen mass ratio according to deinking are 10～15: 100, softening agent and collagen mass ratio are waste paper fibre and the softening agent that 10～12.5: 100 ratio adds deinking; In 30 ℃～65 ℃ water-bath, fully stir; Be that 10～15: 100 ratio drips linking agent in linking agent and collagen mass ratio then; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5～9.7; Under 50 ℃～100 ℃ condition, react 0.5h～3h again, and then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material; Linking agent described in the step 2 is LUTARALDEHYDE or N-N ' methylene-bisacrylamide; Described softening agent is USP Kosher or DOP.
Embodiment two: what this embodiment and embodiment one were different is in 65 ℃ water-bath, to react in the step 1.Other is identical with embodiment one.
Embodiment three: this embodiment is different with one of embodiment one or two is that the waste paper fibre and the collagen mass ratio of deinking in the step 2 is 12: 100.Other is identical with one of embodiment one or two.
Embodiment four: this embodiment is different with one of embodiment one to three is that softening agent and collagen mass ratio are 11: 100 in the step 2.Other is identical with one of embodiment one to three.
Embodiment five: this embodiment is different with one of embodiment one to four is that linking agent and collagen mass ratio are 8～9.5: 100 in the step 2.Other is identical with one of embodiment one to four.
Embodiment six: this embodiment is different with one of embodiment one to four is that linking agent and collagen mass ratio are 8.5: 100 in the step 2.Other is identical with one of embodiment one to four.
Embodiment seven: this embodiment is different with one of embodiment one to four is that linking agent and collagen mass ratio are 9: 100 in the step 2.Other is identical with one of embodiment one to four.
Embodiment eight: following with the waste paper fibre (disregard message paper fiber) and the preparation method of discarded leather collagen synthetic composite material in this embodiment: one, the deinking of waste paper fibre is handled: NaOH and disregard message paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the disregard message paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the disregard message paper fiber of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are disregard message paper fiber and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5～9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment nine: the preparation method with not deinking newspaper fiber and discarded leather collagen synthetic composite material in this embodiment is following: with 30g collagen with after 180mL water mixes; According to not deinking newspaper fiber and collagen mass ratio is 10～15: 100, USP Kosher and collagen mass ratio are waste paper fibre and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be 15: 100 ratio dropping LUTARALDEHYDE then in LUTARALDEHYDE and collagen mass ratio; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7; Under 50 ℃ condition, react 0.5h again, and then pour in the mould reaction solution and drying forming, promptly get matrix material.
Embodiment ten: following with the waste paper fibre (disregard message paper fiber) and the preparation method of discarded leather collagen synthetic composite material in this embodiment: one, the deinking of waste paper fibre is handled: NaOH and disregard message paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the disregard message paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; Disregard message paper fiber and collagen mass ratio according to deinking are 10～15: 100, USP Kosher and collagen mass ratio are the disregard message paper fiber and the USP Kosher of 12.5: 100 ratio adding deinking; In 60 ℃ water-bath, fully stir; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 11: following with the waste paper fibre (disregard message paper fiber) and the preparation method of discarded leather collagen synthetic composite material in this embodiment: one, the deinking of waste paper fibre is handled: NaOH and disregard message paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the disregard message paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the disregard message paper fiber of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are disregard message paper fiber and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be that 10～15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 12: following with the waste paper fibre (disregard message paper fiber) and the preparation method of discarded leather collagen synthetic composite material in this embodiment: one, the deinking of waste paper fibre is handled: NaOH and disregard message paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the disregard message paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the disregard message paper fiber of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are disregard message paper fiber and the USP Kosher that 10～12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be that 15: 100 ratio drips LUTARALDEHYDE in 30 minutes time in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 13: the preparation method with waste paper fibre (chancery paper fiber) and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: with H 2O 2Mix in the water-bath that is incorporated in 40 ℃ according to 2.5: 100 mass ratio with the chancery paper fiber and to react 1h, remove impurity and moisture then, the chancery paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the chancery paper fiber of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are chancery paper fiber and the USP Kosher that 11: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5～9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 14: the preparation method with not deinking chancery paper fiber and discarded leather collagen synthetic composite material in this embodiment is following: with 30g collagen with after 180mL water mixes; According to not deinking chancery paper fiber and collagen mass ratio is 10～15: 100, USP Kosher and collagen mass ratio are waste paper fibre and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be 15: 100 ratio dropping LUTARALDEHYDE then in LUTARALDEHYDE and collagen mass ratio; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7; Under 50 ℃ condition, react 0.5h again, and then pour in the mould reaction solution and drying forming, promptly get matrix material.
Embodiment 15: the preparation method with waste paper fibre (chancery paper fiber) and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and chancery paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the chancery paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; Chancery paper fiber and collagen mass ratio according to deinking are 10～15: 100, USP Kosher and collagen mass ratio are the chancery paper fiber and the USP Kosher of 12.5: 100 ratio adding deinking; In 60 ℃ water-bath, fully stir; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 16: the preparation method with waste paper fibre (chancery paper fiber) and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and chancery paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the chancery paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the chancery paper fiber of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are chancery paper fiber and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be that 10～15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 17: the preparation method with waste paper fibre (chancery paper fiber) and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and chancery paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the chancery paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the chancery paper fiber of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are chancery paper fiber and the USP Kosher that 10～12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 18: following with the waste paper fibre (disregard message paper fiber) and the preparation method of discarded leather collagen synthetic composite material in this embodiment: one, the deinking of waste paper fibre is handled: NaOH and disregard message paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the disregard message paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the disregard message paper fiber of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are disregard message paper fiber and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Press N then, N '-methylene-bisacrylamide and collagen mass ratio are 10～15: 100 ratio dropping N, N '-methylene-bisacrylamide; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7; Under 50 ℃ condition, react 0.5h again, and then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 19: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: with Na 2SiO 39H 2O and newspaper fiber mix in the water-bath that is incorporated in 65 ℃ according to 3.5: 100 mass ratio and react 1.5h, remove impurity and moisture then, the newspaper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the newspaper fiber of deinking and collagen mass ratio is that 12: 100, USP Kosher and collagen mass ratio are newspaper fiber and the USP Kosher that 11: 100 ratio adds deinking; In 35 ℃ water-bath, fully stir; Be that 12: 100 ratio drips linking agent in linking agent and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5, under 60 ℃ condition, reacts 1.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material; Linking agent described in the step 2 is LUTARALDEHYDE or N, N '-methylene-bisacrylamide.
Embodiment 20: following with the waste paper fibre (disregard message paper fiber) and the preparation method of discarded leather collagen synthetic composite material in this embodiment: one, the deinking of waste paper fibre is handled: NaOH and disregard message paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the disregard message paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the disregard message paper fiber of deinking and collagen mass ratio is that 10.17: 100, DOP and collagen mass ratio are disregard message paper fiber and the DOP that 10～12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Press N then, N '-methylene-bisacrylamide and collagen mass ratio are 10～15: 100 ratio dropping N, N '-methylene-bisacrylamide; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7; Under 50 ℃ condition, react 0.5h again, and then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 21: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: with Na 2SiO 39H 2O and newspaper fiber mix in the water-bath that is incorporated in 65 ℃ according to 3.5: 100 mass ratio and react 1.5h, remove impurity and moisture then, the newspaper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the newspaper fiber of deinking and collagen mass ratio is that 12: 100, softening agent and collagen mass ratio are newspaper fiber and the softening agent that 11: 100 ratio adds deinking, in 35 ℃ water-bath, fully stirs, and presses N then; N '-methylene-bisacrylamide and collagen mass ratio are that 12: 100 ratio drips N; N '-methylene-bisacrylamide, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5, under 60 ℃ condition, reacts 1.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material; Softening agent described in the step 2 is USP Kosher or DOP.
Embodiment 22: the preparation method with waste paper fibre (chancery paper fiber) and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and chancery paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the chancery paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the chancery paper fiber of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are chancery paper fiber and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Press N then; N '-methylene-bisacrylamide and collagen mass ratio are that 10～15: 100 ratio drips N-N ' methylene-bisacrylamide, and using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 50 ℃ condition, reacts 0.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 23: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: with Na 2SiO 39H 2O and chancery paper fiber mix in the water-bath that is incorporated in 65 ℃ according to 3.5: 100 mass ratio and react 1.5h, remove impurity and moisture then, the chancery paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the chancery paper fiber of deinking and collagen mass ratio is that 12: 100, USP Kosher and collagen mass ratio are chancery paper fiber and the USP Kosher that 11: 100 ratio adds deinking; In 35 ℃ water-bath, fully stir; Be that 12: 100 ratio drips linking agent in linking agent and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5, under 60 ℃ condition, reacts 1.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material; Linking agent described in the step 2 is LUTARALDEHYDE or N, N '-methylene-bisacrylamide.
Embodiment 24: the preparation method with waste paper fibre (chancery paper fiber) and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and chancery paper fiber are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the chancery paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the chancery paper fiber of deinking and collagen mass ratio is that 10.17: 100, octyl phthalate and collagen mass ratio are chancery paper fiber and the DOP that 10～12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Press N then, N '-methylene-bisacrylamide and collagen mass ratio are 10～15: 100 ratio dropping N, N '-methylene-bisacrylamide; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7; Under 50 ℃ condition, react 0.5h again, and then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Embodiment 25: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: with Na 2SiO 39H 2O and chancery paper fiber mix in the water-bath that is incorporated in 65 ℃ according to 3.5: 100 mass ratio and react 1.5h, remove impurity and moisture then, the chancery paper fiber of deinking; Two, with 30g collagen with after 180mL water mixes; According to the chancery paper fiber of deinking and collagen mass ratio is that 12: 100, softening agent and collagen mass ratio are chancery paper fiber and the softening agent that 11: 100 ratio adds deinking, in 35 ℃ water-bath, fully stirs, and presses N then; N '-methylene-bisacrylamide and collagen mass ratio are that 12: 100 ratio drips N; N '-methylene-bisacrylamide, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5, under 60 ℃ condition, reacts 1.5h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material; Softening agent described in the step 2 is USP Kosher or DOP.
Embodiment 26: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and waste paper fibre are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the waste paper fibre of deinking; Two, with 30g collagen with after 180mL water mixes; According to the waste paper fibre of deinking and collagen mass ratio is that 10.17: 100, USP Kosher and collagen mass ratio are waste paper fibre and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.0, under 60 ℃ condition, reacts 1h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Waste paper fibre in this embodiment is for being raw material with the old and useless newspaper.
The tensile strength with waste paper fibre and discarded leather collagen synthetic matrix material that this embodiment obtains reaches 2.54MPa, and Young's modulus reaches 0.01GPa, and swelling ratio is 31.20%.
Embodiment 27: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and waste paper fibre are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the waste paper fibre of deinking; Two, with 30g collagen with after 180mL water mixes; According to the waste paper fibre of deinking and collagen mass ratio is that 10: 100, USP Kosher and collagen mass ratio are waste paper fibre and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir 1h; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 60 ℃ condition, reacts 1h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Waste paper fibre in this embodiment is for being raw material with the old and useless newspaper.
The tensile strength with waste paper fibre and discarded leather collagen synthetic matrix material that this embodiment obtains reaches 5.06MPa, and Young's modulus reaches 0.05Gpa, and swelling ratio is 25.57%.
Embodiment 28: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: with Na 2SiO 39H 2O and waste paper fibre mix in the water-bath that is incorporated in 60 ℃ according to 3.0: 100 mass ratio and react 1h, remove impurity and moisture then, the waste paper fibre of deinking; Two, with 30g collagen with after 180mL water mixes; According to the waste paper fibre of deinking and collagen mass ratio is that 10: 100, USP Kosher and collagen mass ratio are waste paper fibre and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir 1h; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 60 ℃ condition, reacts 1h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Waste paper fibre in this embodiment is for being raw material with the old and useless newspaper.
The tensile strength with waste paper fibre and discarded leather collagen synthetic matrix material that this embodiment obtains reaches 4.79MPa, and Young's modulus reaches 0.03GPa, and swelling ratio is 24.00%.
Embodiment 29: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and waste paper fibre are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the waste paper fibre of deinking; Two, with 30g collagen with after 180mL water mixes; According to the waste paper fibre of deinking and collagen mass ratio is that 10: 100, USP Kosher and collagen mass ratio are waste paper fibre and the USP Kosher that 1: 10 ratio adds deinking; In 60 ℃ water-bath, fully stir 1h; Be that 15: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 60 ℃ condition, reacts 1h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Waste paper fibre in this embodiment is for being raw material with the old and useless newspaper.
The product tensile strength with waste paper fibre and discarded leather collagen synthetic matrix material that this embodiment obtains reaches 4.31MPa, and Young's modulus reaches 0.06Gpa, and swelling ratio is 20.63%.
Embodiment 30: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and waste paper fibre are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1: 50 mass ratio; Remove impurity and moisture then, get the waste paper fibre of deinking; Two, with 30g collagen with after 180mL water mixes; According to the waste paper fibre of deinking and collagen mass ratio is that 10: 100, USP Kosher and collagen mass ratio are waste paper fibre and the USP Kosher that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir 1h; Be that 12.5: 100 ratio drips LUTARALDEHYDE in LUTARALDEHYDE and collagen mass ratio then, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 60 ℃ condition, reacts 1h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Waste paper fibre in this embodiment is for being raw material with the old and useless newspaper.
The tensile strength with waste paper fibre and discarded leather collagen synthetic matrix material that this embodiment obtains reaches 4.98MPa, and Young's modulus reaches 0.09GPa, and swelling ratio is 12.5%.
The embodiment hentriaconta-: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and waste paper fibre are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the waste paper fibre of deinking; Two, with 30g collagen with after 180mL water mixes; According to the waste paper fibre of deinking and collagen mass ratio is that 1: 10, USP Kosher and collagen mass ratio are waste paper fibre and the USP Kosher that 12.5: 100 ratio adds deinking, in 60 ℃ water-bath, fully stirs 1h, presses N then; N '-methylene-bisacrylamide and collagen mass ratio are that 1: 10 ratio drips N; N '-methylene-bisacrylamide, using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7, under 60 ℃ condition, reacts 1h again; And then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Waste paper fibre in this embodiment is for being raw material with the old and useless newspaper.
Embodiment 32: the preparation method with waste paper fibre and discarded leather collagen synthetic composite material in this embodiment is following: one, the deinking of waste paper fibre is handled: NaOH and waste paper fibre are reacted 1h according to mixed being incorporated in 60 ℃ the water-bath of 1.5: 100 mass ratio; Remove impurity and moisture then, get the waste paper fibre of deinking; Two, with 30g collagen with after 180mL water mixes; According to the waste paper fibre of deinking and collagen mass ratio is that 1: 10, DOP and collagen mass ratio are waste paper fibre and the DOP that 12.5: 100 ratio adds deinking; In 60 ℃ water-bath, fully stir 1h; Press N then, N '-methylene-bisacrylamide and collagen mass ratio are that 1: 10 ratio drips N, N '-methylene-bisacrylamide; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 9.7; Under 60 ℃ condition, react 1h again, and then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material.
Waste paper fibre in this embodiment is for being raw material with the chancery paper fiber.
The matrix material of embodiment hentriaconta-preparation and the matrix material of this embodiment preparation are carried out the soil degrading experiment, and the result is following:

Claims (4)

1. with the preparation method of waste paper fibre and discarded leather collagen synthetic composite material, it is characterized in that with the preparation method of waste paper fibre and discarded leather collagen synthetic composite material following: one, the deinking of waste paper fibre is handled: with NaOH, H 2O 2, Na 2SiO 39H 2O and waste paper fibre are according to 1～3.5: 100 mass ratio mixes in the water-bath that is incorporated in 60 ℃～70 ℃ and reacts 1h～1.5h, removes impurity and moisture then, gets the waste paper fibre of deinking; Two, with after collagen and the mixed of water according to 1g: 6mL; Waste paper fibre and collagen mass ratio according to deinking are 10～15: 100, softening agent and collagen mass ratio are waste paper fibre and the softening agent that 10～12.5: 100 ratio adds deinking; In 30 ℃～65 ℃ water-bath, fully stir; Be that 10～15: 100 ratio drips linking agent in linking agent and collagen mass ratio then; Using mass concentration simultaneously is that 30% aqueous sodium hydroxide solution is regulated pH value to 8.5～9.7; Under 50 ℃～100 ℃ condition, react 0.5h～3h again, and then pour in the mould reaction solution and drying forming, promptly be able to waste paper fibre and discarded leather collagen synthetic matrix material; Linking agent described in the step 2 is LUTARALDEHYDE or N, N '-methylene-bisacrylamide; Described softening agent is USP Kosher or DOP.
2. according to the said preparation method of claim 1, it is characterized in that in 65 ℃ water-bath, reacting in the step 1 with waste paper fibre and discarded leather collagen synthetic composite material.
3. according to claim 1 or 2 said preparing methods, it is characterized in that the waste paper fibre of deinking in the step 2 and collagen mass ratio are 12: 100 with waste paper fibre and discarded leather collagen synthetic composite material.
4. according to claim 1 or 2 said preparing methods, it is characterized in that softening agent and collagen mass ratio are 11: 100 in the step 2 with waste paper fibre and discarded leather collagen synthetic composite material.
CN201110108941A 2011-04-28 2011-04-28 Preparation method for synthesizing composite material by using fiber of waste paper and collagen of waste leather Expired - Fee Related CN102286204B (en)

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