CN103627367A - Environment-friendly adhesive as well as preparation method and application thereof - Google Patents
Environment-friendly adhesive as well as preparation method and application thereof Download PDFInfo
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- CN103627367A CN103627367A CN201310617742.4A CN201310617742A CN103627367A CN 103627367 A CN103627367 A CN 103627367A CN 201310617742 A CN201310617742 A CN 201310617742A CN 103627367 A CN103627367 A CN 103627367A
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Abstract
The invention belongs to the technical field of adhesive production, and particularly relates to an environment-friendly adhesive and a method for preparing the environment-friendly adhesive by using silkworm cocoon waste silk glue. The preparation method of the environment-friendly adhesive comprises the following steps: (1) collecting wastewater generated after boiling silkworm cocoons, cooling to room temperature, then filtering by using an ultrafiltration membrane, and recovering a trapped liquid so as to obtain a silk glue concentrated solution, or concentrating by 10-12 times in vacuum or at normal pressure under the condition of lower than 80 DEG C so as to obtain a silk glue concentrated solution; (2) carrying out modified treatment on the silk glue concentrated solution obtained in the step (1) so as to obtain the silk glue concentrated solution subjected to modified treatment; and (3) concentrating the silk glue concentrated solution subjected to modified treatment at a normal pressure or in vacuum under the condition of lower than or equal to 80 DEG C so as to obtain a sticky flowable material which is the environment-friendly adhesive. The environment-friendly adhesive prepared by the method can be widely applied to wood industries or plant fiber molding industries, is safe and environment-friendly and does not release harmful substances such as formaldehyde which are harmful to human bodies in a using process.
Description
Technical field
The invention belongs to the production technical field of adhesive, and in particular to a kind of environment-protective adhesive and the method for preparing the environment-protective adhesive using silk cocoon waste silk glue, further relate to the application of the environment-protective adhesive.
Background technology
At present, China's Silk quality production scale ranks first in the world, and produces 500000 tons or so of silk cocoon per year, and more than 70,000 tons of raw silk accounts for the 80% and 60% of world production total amount, silk yield accounts for 45% or so of whole world total output.But, the huge wasting of resources is there is in the post-processing of current silk cocoon, silkworm raiser's silk boiling, select silkworm and raw silk processing in, only 0.8 kilogram or so of per kilogram silk cocoon can reach cocoon quality requirement of getting on the bus, the leftover bits and pieces silk cocoon that there are about 20% is discharged into environment without further utilize as waste, is mainly manifested in：In the processing of part silk boiling, raw silk and silk, because the throwing textile technology of China's Traditional Silk industry only utilizes the internal layer fibroin part of silk, and outer layer silk gum is progressively removed, environment is discharged into waste water, silk cocoon is a kind of high protein long fibrous materials, and wherein outer layer sericin averagely accounts for the 20 ~ 30% of silk cocoon gross weight, directly discharge or discard such as without processing, on the one hand the pollution of environment can be caused, is on the other hand also the huge waste to resource, directly affects the economic benefit of industry.
Wherein, sericin is a kind of excellent natural macromolecular material of biocompatibility, content in silk is 20% ~ 30%, its internal layer fibroin to silk plays protection and adhesive action, but the need for being due to throwing and textile technology, sericin is final or is taken off by cleaning, this not only causes the waste of sericin, also result in the pollution of environment, therefore, recovery and exploitation to sericin just turn into the emphasis that numerous researchers are studied, because sericin has unique physicochemical property, it is such as readily soluble, water suction, gelation, it may modify and the characteristic such as anti-oxidant, current sericin is in cosmetics, fibrous material, medicine and other fields are suffered from being widely applied and also made some progress, but it is used as the exploration of environment-friendly adhesive and has no report.
With the reduction of world forest resources, natural timber yield drastically declines, it is used as the substitute of wood --- various artificial boards are increasingly paid attention to by people, ended for the end of the year 2008, existing artificial board enterprise family more than 6 000 of China, production scale is more than 9 000 ten thousand steres, as the first big country of world's Wood-based Panel Production and consumption, no matter domestic or external, adhesive is very big in the consumption of wood industry, it is also simultaneously wood-based plate quality, the determinant of technology, has statistics to show, it accounts for more than the 3/4 of the total consumption of adhesive.China's based Wood Adhesives yield reaches 5,000,000 tons in 2010, ranks first in the world.
At present, China's timber industry is main with " three-aldehyde glue "-urea-formaldehyde resin adhesive（UF）, phenolic resin glue（PF）And melamine-formaldehyde resin adhesive（MF）Based on, such as, about 1,400,000 tons of the total consumption of China's wood adhesive in 2005（It is dry）, wherein nearly 1,390,000 tons of urea-formaldehyde resin adhesive consumption（It is dry）, account for absolute leading position, only about 1.6 ten thousand tons of phenolic resin glue consumption（It is dry）.The intermolecular ehter bond of urea-formaldehyde glue（-CH2-O-CH2-）It is easily broken off in the case of damp and hot and discharges free formaldehyde；Melamine-formaldehyde resin adhesive also can release formaldehyde, and production cost is higher；Though isocyanates adhesive will not discharge free formaldehyde, but expensive, work progress toxicity is big, these synthetic adhesives are due to during production or use, it can discharge to the harmful substance such as environment and the harmful formaldehyde of human body, and its raw material sources is in non-renewable fossil resource, concern and the reduction of petroleum reserves since 1990s with people to itself and environmental security, make this problem more protrude, in the urgent need to the exploitation reproducible environment-protective adhesive of one class.
The content of the invention
It is an object of the invention to the adhesive raw material sources for solving prior art are limited, production cost is high, the deficiency of the harmful substance such as easy release formaldehyde during production or use, a kind of environment-protective adhesive is provided, the environment-protective adhesive is prepared from using silk cocoon waste silk glue and other leftover bits and pieces.
It is a further object to provide a kind of preparation method of environment-protective adhesive.
It is a still further object of the present invention to provide a kind of application of environment-protective adhesive.
To achieve the above object of the invention, the technical solution adopted by the present invention is as follows：
A kind of preparation method of environment-protective adhesive, the preparation method comprises the following steps：
（1）The waste water after silk cocoon is boiled in collection, is cooled to room temperature, then with ultrafiltration membrance filter, is reclaimed trapped fluid and is obtained silk gum concentrate, or under the conditions of less than 80 DEG C, vacuum or normal pressure concentrate 10 ~ 12 times, obtain silk gum concentrate；
（2）By step（1）The silk gum concentrate of acquisition is modified processing, obtains the silk gum concentrate after modification；
（3）By step（2）Silk gum concentrate after modification normal pressure or vacuum concentration under the conditions of≤80 DEG C again, obtain thick flowable material, as environment-protective adhesive finished product.
Above step（1）In the waste water boiled after silk cocoon refer to that peasant household reels off raw silk from cocoons Cocoon, tussah cocoon, castor-oil plant silk cocoon and other silk cocoon high temperature scourings the waste liquid of generation, retains useless silkworm cocoon therein, useless silk cocoon clothing, waste silk；Milipore filter used（UF）Refer to that aperture is not more than 1 μm of filter membrane, filter type can use gravity filtration or pressure filtration；
Above step（2）In modification one of for following three method of modifying, three kinds of methods can obtain the adhesive of different adhesive properties：
（1）Heat modification：By step（1）Silk gum concentrate reaction 30min is stirred under the conditions of 85 DEG C, until micro-bubble occurs in whipping process in silk gum concentrate, obtain the silk gum concentrate after the modification of inclined brown；
（2）It is urea-modified：By step（1）Silk gum concentrate solution under the conditions of 60 DEG C by 1 ~ 3mol/L addition add urea（Common agricultural urea）Reaction 1h is stirred, the silk gum concentrate after the modification of inclined brown is obtained；Urea-modified is a process for heat absorption, and the amount for adding urea is more, then the crystal that the silk gum concentrate after gained modification is separated out after the cooling period is also more, therefore 1 ~ 3mol/L of selection addition is optimal；
（3）SDS is modified：By step（1）Silk gum concentrate solution at 60 DEG C by mass fraction 0.5 ~ 1% addition add dodecyl sodium sulfate（SDS, chemistry is pure）Stirring reaction 1h is obtained with frothy brown liquid, and after after its cooling, liquid is in light brown and with cotton-shaped or mucilage binding material, the silk gum concentrate as after modification；SDS addition is reasonable in design in the present invention, although the SDS of excessive addition can cause the solid content to increase, can not improve the viscosity of gained environment-protective adhesive, cause wastage of material.
Above step（3）In evaporating concentration process not concrete regulation cycles of concentration, because the dosage of modifying process, modifying agent is different, so being defined to obtain sticky mass, specifically can re-refine or add other additives according to practical use；
Steps described above（1）And step（3）In Rotary Evaporators be laboratory common Rotary evaporator, additional can vacuumize or not vacuumize, it is also possible to it is other evaporation and concentration facilities, equipment replace.
Environment-protective adhesive prepared by preparation method of the present invention can be widely applied in wood industry and formed by plant fibre industry, and safety and environmental protection will not discharge the harmful substances such as harmful formaldehyde during use.
The present invention has following beneficial effect：
（1）The present invention will boil the waste water after silk cocoon and turn waste into wealth, improve the utilization rate and economic worth of cocoon sericin albumen, it is to avoid the waste of resource, reduces the discharge of discarded object, reduces the pollution to environment.
（2）Environment-protective adhesive safety and environmental protection prepared by the present invention, will not discharge the harmful substances such as harmful formaldehyde, have a wide range of application during use.
（3）The preparation method of the present invention is simple to operate, and extensively, working condition is gentle, it is easy to industrialized production for raw material sources.
Embodiment
With reference to specific embodiment, technical scheme is further described：
Raw material：Common silkworm variety, the silk cocoon waste liquid behind Zhejiang Tongxiang, kiering of reeling off raw silk from cocoons is the silk cocoon waste silk glue described in the present invention, is cooled to room temperature standby.
Environment-protective adhesive viscosity measurement：With reference to GB/T 2794-2013；
Tensile strength（Bonding strength）The method of inspection：Tested with reference to ASTM D1037-99,21-27.
Embodiment 1
A kind of preparation method of environment-protective adhesive, methods described comprises the following steps：
（1）The milipore filter in 1 μm of aperture is fixed in upper vessel portion, 30L silk cocoon waste silk glues gravity filtration 12 hours is taken, filter membrane top slightly sticky liquid, as silk gum concentrate are collected in top stirring；
（2）Above-mentioned silk gum concentrate is put into beaker, is put into thermostat water bath, is during which stirred continuously, water bath with thermostatic control pot temperature is set as after 85 DEG C, about 30min that silk gum concentrate starts micro-bubble occur, continue to stir 10min, obtain nearly brown liquid, the silk gum concentrate as after modification；
（3）Silk gum concentrate after above-mentioned modification is moved into rotary evaporation bottle, atmospheric evaporation is concentrated under the conditions of 80 DEG C, until the silk gum concentrate after modification becomes sticky, but it is flowable, viscous fluid is collected, room temperature is cooled to and obtains environment-protective adhesive finished product；
Its viscosity of environment-protective adhesive made from embodiment 1 is 53000 ± 500mP.s, and tensile strength is 1.2 ± 0.05MPa.
Embodiment 2
（1）The filter membrane in 0.8 μm of aperture is fixed in upper vessel portion, 30L silk cocoon waste silk glues are taken, filtered 8 hours under 0.05Mpa pressure, filter membrane top slightly sticky liquid, as silk gum concentrate are collected in top stirring；
（2）Above-mentioned silk gum concentrate is put into beaker, is put into thermostat water bath, water bath with thermostatic control pot temperature is set as 60 DEG C, urea granules are added by 1mol/L addition（Agricultural fertilizer）, stirring and dissolving after about 1 hour, starts to crystallize, the silk gum concentrate as after modification in solution；
（3）Silk gum concentrate after above-mentioned modification is moved into rotary evaporation bottle, concentration is evaporated under reduced pressure under the conditions of vacuum -0.07Mpa, temperature 60 C, until the silk gum concentrate after modification becomes sticky, but it is flowable, viscous fluid is collected, room temperature is cooled to and obtains environment-protective adhesive finished product；
Its viscosity of environment-protective adhesive made from embodiment 2 is 54000 ± 500 mP.s, and tensile strength is 1.4 ± 0.05 MPa.
Embodiment 3
（1）The filter membrane in 0.8 μm of aperture is fixed in upper vessel portion, 30L silk cocoon waste silk glues are taken, filtered 8 hours under 0.05Mpa pressure, filter membrane top slightly sticky liquid, as silk gum concentrate are collected in top stirring；
（2）Above-mentioned silk gum concentrate is put into beaker, is put into thermostat water bath, water bath with thermostatic control pot temperature is set as 60 DEG C, urea granules are added by 3mol/L addition（Agricultural fertilizer）, stirring and dissolving after about 1 hour, starts to crystallize, the silk gum concentrate as after modification in solution；
（3）Silk gum concentrate after above-mentioned modification is moved into rotary evaporation bottle, concentration is evaporated under reduced pressure under the conditions of vacuum -0.05Mpa, temperature 70 C, until the silk gum concentrate after modification becomes sticky, but it is flowable, viscous fluid is collected, room temperature is cooled to and obtains environment-protective adhesive finished product；
Its viscosity of environment-protective adhesive made from embodiment 3 is 55000 ± 500mP.s, and tensile strength is 1.3 ± 0.05MPa.
Embodiment 3
（1）The above-mentioned silk cocoon waste silk glues of 30L are taken under the conditions of 70 DEG C, normal pressure concentrates 10 times, silk gum concentrate is made；
（2）Above-mentioned silk gum concentrate is put into beaker, is put into thermostat water bath, water bath with thermostatic control pot temperature is set as 60 DEG C, 0.5% addition adds SDS by weight percent（Commercially available reagent, chemistry is pure）, stirring and dissolving after about 1 hour, starts floccule occur, the silk gum concentrate as after modification in solution；
（3）Silk gum concentrate after above-mentioned modification is moved into rotary evaporation bottle, atmospheric evaporation is concentrated at 70 DEG C, until the silk gum concentrate after modification becomes sticky, but it is flowable, viscous fluid is collected, room temperature is cooled to and obtains environment-protective adhesive finished product；
55000 ± 500mP.s of its viscosity of environment-protective adhesive made from embodiment 4, tensile strength is 1.4 ± 0.05MPa.
Embodiment 5
（1）The above-mentioned silk cocoon waste silk glues of 30L are taken under the conditions of 60 DEG C, normal pressure concentrates 12 times, silk gum concentrate is made；
（2）Above-mentioned silk gum concentrate is put into beaker, is put into thermostat water bath, water bath with thermostatic control pot temperature is set as 60 DEG C, 1.0% addition adds SDS by weight percent（Commercially available reagent, chemistry is pure）, stirring and dissolving after about 1 hour, starts floccule occur, the silk gum concentrate as after modification in solution；
（3）Silk gum concentrate after above-mentioned modification is moved into rotary evaporation bottle, atmospheric evaporation is concentrated at 72 DEG C, until the silk gum concentrate after modification becomes sticky, but it is flowable, viscous fluid is collected, room temperature is cooled to and obtains environment-protective adhesive finished product；
Its viscosity of environment-protective adhesive made from embodiment 5 is 54500 ± 500mP.s, and tensile strength is 1.4 ± 0.05MPa.
Embodiment described above is a kind of preferably scheme of the present invention, not makees any formal limitation to the present invention, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (8)
1. a kind of preparation method of environment-protective adhesive, it is characterised in that the preparation method comprises the following steps：
（1）The waste water after silk cocoon is boiled in collection, is cooled to room temperature, then with ultrafiltration membrance filter, is reclaimed trapped fluid and is obtained silk gum concentrate, or under the conditions of less than 80 DEG C, vacuum or normal pressure concentrate 10 ~ 12 times, obtain silk gum concentrate；
（2）By step（1）The silk gum concentrate of acquisition is modified processing, obtains the silk gum concentrate after modification；
（3）By step（2）Silk gum concentrate after modification normal pressure or vacuum concentration under the conditions of≤80 DEG C again, obtain thick flowable material, as environment-protective adhesive finished product.
2. a kind of preparation method of environment-protective adhesive according to claim 1, it is characterised in that step（1）Aperture≤1 μm of middle milipore filter, filter type is gravity filtration or pressure filtration.
3. a kind of preparation method of environment-protective adhesive according to claim 1 or 2, it is characterised in that step（2）In modification use heat modification：By step（1）Silk gum concentrate reaction 30min is stirred under the conditions of 85 DEG C, until silk gum concentrate occurs being further continued for after micro-bubble stirring 10min in whipping process, obtain the silk gum concentrate after the modification of inclined brown.
4. a kind of preparation method of environment-protective adhesive according to claim 1 or 2, it is characterised in that step（2）In modification using urea-modified：By step（1）Silk gum concentrate solution add urea by 1 ~ 3mol/L addition under the conditions of 60 DEG C and be stirred reaction 1h, obtain the silk gum concentrate after the modification of inclined brown.
5. a kind of preparation method of environment-protective adhesive according to claim 1 or 2, it is characterised in that step（2）In modification using dodecyl sodium sulfate be modified：By step（1）Silk gum concentrate solution add dodecyl sodium sulfate stirring reaction 1h by the addition of mass fraction 0.5 ~ 1% under the conditions of 60 DEG C and obtain with frothy brown liquid, after after its cooling, liquid is in light brown and with cotton-shaped or mucilage binding material, the silk gum concentrate as after modification.
6. environment-protective adhesive prepared by the preparation method described in claim 1 ~ 5 any one.
7. environment-protective adhesive according to claim 6, it is characterised in that the viscosity of the environment-protective adhesive is higher than 50000 mP.s, its tensile strength is higher than 1.0 MPa.
8. application of the environment-protective adhesive in wood industry, formed by plant fibre industry described in claim 6.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699959A (en) * | 2019-10-22 | 2020-01-17 | 江阴市长泾花园毛纺织有限公司 | Manufacturing method of silk rabbit wool polyester blended fabric |
| CN110747565A (en) * | 2019-10-22 | 2020-02-04 | 江阴市长泾花园毛纺织有限公司 | Manufacturing method of silk rabbit wool polyester blended autumn and winter coat fabric |
| CN113563841A (en) * | 2021-07-08 | 2021-10-29 | 苏州绿豪新材料科技有限公司 | Modified vegetable protein adhesive and preparation method thereof |
| CN114702936A (en) * | 2022-05-18 | 2022-07-05 | 广西至善新材料科技有限公司 | Water-based adhesive and preparation method and application thereof |
| CN115772376A (en) * | 2022-11-30 | 2023-03-10 | 浙江理工大学 | Preparation method of environment-friendly glue based on sericin-WPU-polyamide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699959A (en) * | 2019-10-22 | 2020-01-17 | 江阴市长泾花园毛纺织有限公司 | Manufacturing method of silk rabbit wool polyester blended fabric |
| CN110747565A (en) * | 2019-10-22 | 2020-02-04 | 江阴市长泾花园毛纺织有限公司 | Manufacturing method of silk rabbit wool polyester blended autumn and winter coat fabric |
| CN113563841A (en) * | 2021-07-08 | 2021-10-29 | 苏州绿豪新材料科技有限公司 | Modified vegetable protein adhesive and preparation method thereof |
| CN113563841B (en) * | 2021-07-08 | 2022-12-27 | 苏州绿豪新材料科技有限公司 | Modified vegetable protein adhesive and preparation method thereof |
| CN114702936A (en) * | 2022-05-18 | 2022-07-05 | 广西至善新材料科技有限公司 | Water-based adhesive and preparation method and application thereof |
| CN114702936B (en) * | 2022-05-18 | 2023-10-24 | 广西至善新材料科技有限公司 | Water-based adhesive and preparation method and application thereof |
| CN115772376A (en) * | 2022-11-30 | 2023-03-10 | 浙江理工大学 | Preparation method of environment-friendly glue based on sericin-WPU-polyamide |
| CN115772376B (en) * | 2022-11-30 | 2024-04-05 | 浙江理工大学 | Preparation method of environment-friendly glue based on sericin-WPU-polyamide |
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