CN101191039B - Method for preparing paper-making black liquor adhesive - Google Patents
Method for preparing paper-making black liquor adhesive Download PDFInfo
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- CN101191039B CN101191039B CN200610104975A CN200610104975A CN101191039B CN 101191039 B CN101191039 B CN 101191039B CN 200610104975 A CN200610104975 A CN 200610104975A CN 200610104975 A CN200610104975 A CN 200610104975A CN 101191039 B CN101191039 B CN 101191039B
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Abstract
The invention discloses a preparation method for papermaking black liquor adhesive. Ethyleneurea and melamine or polyvinyl alcohol are taken as formaldehyde catching agent, and then added with carbamide, potato starchy residue and lauxite to react to obtain the papermaking black liquor adhesive. The invention on the one hand can lower the formaldehyde release of board and improve the hydrolytic resistance, on the other hand can provide effective approach for the comprehensive utilization of the papermaking black liquid and the lignin extracted from the papermaking black liquid.
Description
Technical field
The present invention relates to a kind of preparation method of environment protection type paper black liquor adhesive, relate in particular to the production method of compound paper-making black liquor adhesive.
Background technology
China is the country of Shaolin, exists bigger contradiction between the timber supply and demand, and the important channel that solves this contradiction is production and the utilization that must greatly develop with the wood-based plate composite sheet that is the center.Produce 1 cubic metre of shaving board, the sheet material that can replace 3.1 cubic metres of logs to make with urea-formaldehyde resin adhesive; And produce 1 ton of fiberboard with urea-formaldehyde resin adhesive, can replace 5.6 cubic metres of former wood-based planets.Be that tackiness agent is significant to improving timber utilization rate; Simultaneously, timber industry also is huge to the consumption of tackiness agent, all will adopt a large amount of tackiness agent aspect the composite sheets such as wood-based plate, glued board, sandwich panel, cored slab, sewing machine table, wood plastic composite, wooden alloy sheets.For example: produce 10000 cubic metres of glued boards and need 1000 tons of tackiness agent.
This shows, in the production of composite sheet, to consume a large amount of tackiness agent, and use maximum in these are gluing is urea-formaldehyde resin adhesive, it has adhesiveproperties preferably, its sticking strong strength ratio animal and plant glue height, photostabilization is good and be applicable to the viscose glue production of composite sheets such as timber, glued board, veneer sheet and bamboo and wood products, the more important thing is that its price comparison is low and is widely used.And these composite sheet goods are widely used in places such as family that people hang up one's hat, live and office.But, exist a certain amount of free formaldehyde in these tackiness agent or the composite sheet goods, for example, free formaldehyde content in the urea-formaldehyde resin adhesive is up to 3-5%, because of it give off poisonous gas in process for processing and use-formaldehyde, severe contamination infringement people's is healthy, should be very restricted in the use.But, still also can't limit its use effectively at present, and develop into uncontrollable situation.Therefore, develop, application low formaldehyde content composite sheet sticks with glue agent or do not have the free formaldehyde composite sheet becomes the task of top priority, and seem very necessary.The present invention has developed low content of free formaldehyde content, and the low-cost composite sheet tackiness agent of compliance with environmental protection requirements, and make it keep every premium properties of urea-formaldehyde resin adhesive, and reduce its production cost, make the practical tackiness agent that each composite sheet processing enterprise can bear fully.
China formulated GB18580-2001 " indoor decorating material wood-based plate and goods formaldehyde thereof discharge and limits the quantity of ", GB18583-2001 ten mandatory national standards such as " limits of harmful substances in the indoor decorating adhesive " December calendar year 2001, from compulsory execution on July 1 in 2002.New standard is very low to the free formaldehyde release restriction, and the wood-based plate that China produces at present still is difficult to the national standard requirement that reaches new, this mainly has been to use the cause of the high urea-formaldehyde resin adhesive of free formaldehyde content, also is present insoluble great technical barrier.And new standard does not reach the basic demand of protection HUMAN HEALTH yet to free formaldehyde release restriction, exist continue to reduce may or requirement.
Summary of the invention
The purpose of this invention is to provide a kind of tackiness agent that utilizes the burst size of methanal that can reduce sheet material of black liquid manufacturing and improve its water resistance.
Above-mentioned paper-making black liquor adhesive is to be made by following steps:
One, in the 500ml container, add 0.15 part of polycondensation agent, add 1.56 parts of black liquids when being warmed up to 40 ℃～50 ℃, stir and add 0.16 part of catalyzer down, reaction was 30 minutes when the temperature of solution remained on 45 ℃～55 ℃, 0.50 part in the formaldehyde of adding 36% in solution, reaction was 30 minutes when the temperature of solution remained on 45 ℃～55 ℃, in 30 minutes, solution is warmed up to 80 ℃～85 ℃ then, add 0.30 part～0.40 part in 36% formaldehyde again, stirring reaction is 120 minutes in the time of 80 ℃～85 ℃, in 30 minutes, solution is warmed up to 85 ℃～95 ℃, solution kept this temperature 10 minutes, in 20 minutes solution was cooled to 80 ℃～85 ℃ then, kept this temperature 40 minutes, add 0.50 part～0.80 part black liquid again, the temperature of solution remains on 80 ℃～85 ℃ stirring reactions and made virgin rubber in 30 minutes;
Two, add 0.06 part～0.10 part of methanal trapping agent in 1 part of virgin rubber that step 1 makes, stirring reaction was 30 minutes when the temperature of solution remained on 80 ℃～85 ℃;
Three, add 0.05 part～0.10 part of potato starchy residue in the jelly that step 2 is made again, stirring reaction made paper-making black liquor adhesive in 30 minutes under the room temperature.
Above-mentioned polycondensation agent is a phenol, and catalyzer is a sodium hydroxide, and methanal trapping agent is urea, ethylene group urea or trimeric cyanamide.
Above-mentioned paper-making black liquor adhesive can reduce the burst size of methanal of sheet material on the one hand and improve its water resistance, can find effective way for the comprehensive utilization of black liquid or the xylogen that extracts on the other hand from black liquid.At present, black liquid has surpassed all pollutions to the pollution of environment, and developing into first source of pollution, particularly black liquid gradually is catastrophic to the destruction of water quality.This research project successfully sticks with glue agent with black liquid or the xylogen that extracts as the preparation composite sheet from black liquid, and formed the low-cost environment-friendly composite sheet and sticked with glue new technology that agent produces, novel process, newly prescription and novel method, changed present production status, the advantage that should have two aspects at least: one, can produce low content of free formaldehyde content composite sheet and stick with glue agent, for indoor decorating already provides the composite sheet of no free formaldehyde content, improve indoor environment.They are two years old, produce the same tackiness agent of composite sheet with the black liquid xylogen, being the behavior provides the raw material of cheapness and wide material sources, solved of the pollution problem of the black liquid of papermaking enterprise again, for effective way has been found in the comprehensive utilization of the xylogen that extracts in black liquid or the black liquid to environment.
Low-cost environment-friendly composite sheet Study on making adhesives success is for composite sheet manufacturing and upholstery industry provide primary condition.And the continuous increase of the compulsory execution of national new standard and people's Environmental awareness provides opportunity for applying of low-cost environment-friendly composite sheet tackiness agent again.Therefore, the popularizing application prospect of this project is very wide, also can produce huge economic and social benefit.And this project has little, the instant effect of investment again, adapts to the characteristics that the medium-sized and small enterprises tissue is produced, and the production equipment of now producing urea-formaldehyde resin or synvaren need not to change can organize production.
The formation principle of synvaren is: in the presence of alkali, the contraposition of phenolic hydroxyl group and two adjacent hydrogen and formaldehyde reaction in the phenol molecule generate the isomer of various hydroxymethyl phenols.
The hydroxymethyl phenol isomer that is generated, except can continue and phenol reactant, also can generate the poly-hydroxy sylvan with formaldehyde reaction.
Various hydroxymethyl phenols can react to each other, also can with phenol, aldehyde reaction, form initial stage resol, polycondensation further takes place then, and to obtain molecular structure be the netted final form of resol.
Major ingredient in the black liquid is xylogen and alkali, and the agent structure of xylogen is thought at present based on phenylpropyl alcohol alkane, and has only three kinds of basic structures (non-condensed type structure), that is:
Guaiacyl structure Syringa oblata Lindl. based structures is to the hydroxyl based structures
There is more hydroxyl in the lignin structure, exists with alcoholic extract hydroxyl group and two kinds of forms of phenolic hydroxyl group.In the presence of alkali, xylogen has the reaction that generates methylol with formaldehyde, comprises two aspects, and the one, the methylol reaction can take place on the room that exists on the xylogen aromatic ring, the 2nd, on the aromatic ring side switch also hydroxymethylation can take place.Therefore, theoretically, the composite sheet tackiness agent free formaldehyde content that makes with black liquid is very low or do not have free formaldehyde and exist, and water tolerance should be fine.Simultaneously, this basic structure and reaction be also for black liquid can be used in the preparation paper-making black liquor adhesive, and be used to make composite sheet and created primary condition.
Contain poly-hydroxy in the potato starchy residue, they can form acetal with free formaldehyde, thereby prevent that free formaldehyde from discharging into air, reduce and pollute.Simultaneously, C in the glucose unit in paper-making black liquor adhesive and potato starchy residue or the potato starchy residue molecular structure
6On aldehyde radical, in the hot-press solidifying stage of board materials production, reaction generates hemiacetal and acetal, forms crosslinked three dimensional structure, so can increase the bond strength and the water tolerance of glue.In addition, it can also add in the glue as filler, and its filling effect can reduce the volumetric shrinkage of glue-line, shrinks the pressure that produces thereby reduce with volume.And can improve the solid content of product, and remove the vacuum hydro-extraction operation in the former technology, make raw material consumption and process cost reduce simultaneously.
Embodiment
Embodiment 1
One, in the 500ml container, add phenol 15g, add the 156g black liquid when being warmed up to 40 ℃, stir and add 16g sodium hydroxide down, reaction was 30 minutes when the temperature of solution remained on 45 ℃, the formaldehyde 50g of adding 36% in solution, reaction was 30 minutes when the temperature of solution remained on 45 ℃, in 30 minutes, solution is warmed up to 80 ℃ then, add 36% formaldehyde 30g again, stirring reaction is 120 minutes in the time of 80 ℃, the reaction back was warmed up to 85 ℃ with solution in 30 minutes, solution kept this temperature 10 minutes, in 20 minutes solution was cooled to 80 ℃ then, kept this temperature 40 minutes, add the 50g black liquid again, the temperature of solution remains on 80 ℃ of stirring reactions and made virgin rubber in 30 minutes;
Two, add urea 6g in 1 part of virgin rubber that step 1 makes, stirring reaction was 30 minutes when the temperature of solution remained on 80 ℃;
Three, add potato starchy residue 5g again in the jelly that step 2 is made, stirring reaction made paper-making black liquor adhesive in 30 minutes under the room temperature.
Embodiment 2
One, in the 500ml container, add phenol 15g, add the 156g black liquid when being warmed up to 50 ℃, stir and add 16g sodium hydroxide down, reaction was 30 minutes when the temperature of solution remained on 55 ℃, the formaldehyde 50g of adding 36% in solution, the temperature of solution remains on 55 ℃ of reactions 30 minutes, in 30 minutes, solution is warmed up to 85 ℃ then, add 36% formaldehyde 40g again, stirring reaction is 120 minutes in the time of 85 ℃, in 30 minutes, solution is warmed up to 95 ℃, solution kept this temperature 10 minutes, in 20 minutes solution was cooled to 85 ℃ then, kept this temperature 40 minutes, add the 80g black liquid after 40 minutes again, the temperature of solution remains on 85 ℃ of stirring reactions and made virgin rubber in 30 minutes;
Two, add ethylene group urea 10g in 1 part of virgin rubber that step 1 makes, stirring reaction was 30 minutes when the temperature of solution remained on 85 ℃;
Three, add potato starchy residue 10g again in the jelly that step 2 is made, stirring reaction made paper-making black liquor adhesive in 30 minutes under the room temperature.
Embodiment 3
One, in the 500ml container, add phenol 15g, add the 156g black liquid when being warmed up to 40 ℃, stir and add 16g sodium hydroxide down, reaction was 30 minutes when the temperature of solution remained on 45 ℃, the formaldehyde 50g of adding 36% in solution, reaction was 30 minutes when the temperature of solution remained on 45 ℃, in 30 minutes, solution is warmed up to 80 ℃ then, add 36% formaldehyde 40g again, stirring reaction is 120 minutes in the time of 80 ℃, the reaction back was warmed up to 85 ℃ with solution in 30 minutes, solution kept this temperature 10 minutes, in 20 minutes solution was cooled to 80 ℃ then, kept this temperature 40 minutes, add the 80g black liquid after 40 minutes again, the temperature of solution remains on 80 ℃ of stirring reactions and made virgin rubber in 30 minutes;
Two, add trimeric cyanamide 10g in 1 part of virgin rubber that step 1 makes, stirring reaction was 30 minutes when the temperature of solution remained on 80 ℃;
Three, add potato starchy residue 10g again in the jelly that step 2 is made, stirring reaction made paper-making black liquor adhesive in 30 minutes under the room temperature.
The paper-making black liquor adhesive analytical results:
Claims (1)
1. the preparation method of a paper-making black liquor adhesive, it is characterized in that: it is to be made by following steps,
One, in the 500ml container, add 0.15 part of polycondensation agent, add 1.56 parts of black liquids when being warmed up to 40 ℃～50 ℃, stir and add 0.16 part of catalyzer down, reaction was 30 minutes when the temperature of solution remained on 45 ℃～55 ℃, 0.50 part in the formaldehyde of adding 36% in solution, reaction was 30 minutes when the temperature of solution remained on 45 ℃～55 ℃, in 30 minutes, solution is warmed up to 80 ℃～85 ℃ then, add 0.30 part～0.40 part in 36% formaldehyde again, stirring reaction is 120 minutes in the time of 80 ℃～85 ℃, in 30 minutes, solution is warmed up to 85 ℃～95 ℃, solution kept this temperature 10 minutes, in 20 minutes solution was cooled to 80 ℃～85 ℃ then, kept this temperature 40 minutes, add 0.50 part～0.80 part black liquid again, the temperature of solution remains on 80 ℃～85 ℃ stirring reactions and made virgin rubber in 30 minutes;
Two, add 0.06 part～0.10 part of methanal trapping agent in 1 part of virgin rubber that step 1 makes, stirring reaction was 30 minutes when the temperature of solution remained on 80 ℃～85 ℃;
Three, add 0.05 part～0.10 part of potato starchy residue in the jelly that step 2 is made again, stirring reaction made paper-making black liquor adhesive in 30 minutes under the room temperature;
Described polycondensation agent is a phenol, and catalyzer is a sodium hydroxide, and methanal trapping agent is urea, ethylene group urea or trimeric cyanamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200610104975A CN101191039B (en) | 2006-11-20 | 2006-11-20 | Method for preparing paper-making black liquor adhesive |
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| CN200610104975A CN101191039B (en) | 2006-11-20 | 2006-11-20 | Method for preparing paper-making black liquor adhesive |
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| CN101191039A CN101191039A (en) | 2008-06-04 |
| CN101191039B true CN101191039B (en) | 2010-05-12 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544878B (en) * | 2009-05-05 | 2012-01-04 | 浙江林学院 | Alkali lignin oxidized starch modified phenolic glue and production method thereof |
| CN101928536A (en) * | 2010-05-06 | 2010-12-29 | 安吉仕强制胶有限公司 | Flame retardant modified lignin resin glue and preparing method thereof |
| CN102675570A (en) * | 2012-04-30 | 2012-09-19 | 苏州信邦绿色新材料科技有限公司 | Preparation method of modified lignin and starch composite material for phenolic resin adhesive |
| CN104293258B (en) * | 2014-03-10 | 2016-05-18 | 黄淮学院 | A kind of method of papermaking wastewater recycling and the adhesive that adopts the method to produce |
| CN105273666B (en) * | 2015-11-04 | 2017-03-08 | 东莞市胜成粘合剂科技有限公司 | A kind of method preparing composite biomass adhesive using black liquid |
| CN108003822A (en) * | 2017-12-26 | 2018-05-08 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of methylolation Lignin-based phenolic adhesive |
| CN113403026B (en) * | 2021-06-15 | 2023-01-31 | 福建聚星胜科技有限公司 | Aldehyde-free adhesive synthesized from papermaking black liquor and preparation method and application thereof |
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| CN1067437A (en) * | 1991-06-03 | 1992-12-30 | 张利 | A kind of water soluble resin and manufacture method thereof |
| CN1144255A (en) * | 1996-05-24 | 1997-03-05 | 许昌石油助剂厂 | Petroleum production increasing agent and its producing process |
| US5866642A (en) * | 1991-06-13 | 1999-02-02 | Georgia-Pacific Resins, Inc. | Reactive phenolic resin modifier |
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Patent Citations (3)
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|---|---|---|---|---|
| CN1067437A (en) * | 1991-06-03 | 1992-12-30 | 张利 | A kind of water soluble resin and manufacture method thereof |
| US5866642A (en) * | 1991-06-13 | 1999-02-02 | Georgia-Pacific Resins, Inc. | Reactive phenolic resin modifier |
| CN1144255A (en) * | 1996-05-24 | 1997-03-05 | 许昌石油助剂厂 | Petroleum production increasing agent and its producing process |
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| 方继敏，潘婵.草浆造纸黑液用于人造板胶粘剂的研究.粘接第26卷 第1期.2005,第26卷(第1期),12-15. |
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