CN102174159B - Phenol-formaldehyde resin for wet curtain paper and method for preparing same - Google Patents
Phenol-formaldehyde resin for wet curtain paper and method for preparing same Download PDFInfo
- Publication number
- CN102174159B CN102174159B CN201110074525A CN201110074525A CN102174159B CN 102174159 B CN102174159 B CN 102174159B CN 201110074525 A CN201110074525 A CN 201110074525A CN 201110074525 A CN201110074525 A CN 201110074525A CN 102174159 B CN102174159 B CN 102174159B
- Authority
- CN
- China
- Prior art keywords
- phenol
- xylogen
- preparation
- wet curtain
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Paper (AREA)
Abstract
The invention discloses a method for preparing phenol-formaldehyde resin for wet curtain paper, comprising the following steps: adding phenol, formaldehyde, lignin and base to a reaction vessel to carry out condensation reaction, wherein the molar ratio of the phenol to the formaldehyde is 1:(2.0-4.0), the weight of the lignin is 10-60% of that of the phenol, and the weight of the base is 2-8% of that of the phenol, and rapidly cooling to the temperature blow 40 DEG C after the generated resin has the viscosity of 20-50cp/25 DEG C to obtain the phenol-formaldehyde resin. The invention further discloses a method for preparing a piece of wet curtain paper from the phenol-formaldehyde resin. The method adopts lignin which replaces a part of phenol to synthesize the phenol-formaldehyde resin. Because the cost of the lignin is nearly zero, the production cost of the phenol-formaldehyde resin and the wet curtain paper is reduced, and the waste pollution is decreased.
Description
Technical field
The present invention relates to the phenolic resins field, especially a kind of wet curtain paper is used resol, and preparation method thereof.
Background technology
Wet curtain paper, another name cascade paper is honey-combed, is to be formed by the body paper processing.Wet curtain paper is the needed important composition parts of various wet curtain equipment.As:
1, is applied to " wet curtain-negative-pressure air fan " in the cooling system, forms by porous wet curtain paper, water circulation system, fan.Unsaturated airflow when porous, moistening wet curtain paper surface, the large quantity of moisture evaporation, the sensible heat that is embodied by temperature in the air is converted into vaporization heat, thereby reduces the temperature of air self.The freezing air that will pass through Wet-curtain temperature reducing during the fan exhausting is constantly introduced indoor in a steady stream, thereby reaches cooling-down effect.
2, be applied to humidification system, wet curtain paper is used for plantation, greenhouse and some other special industry higher to humidity requirement during as the humidification medium more.Because wet curtain paper has suction, water-fast, characteristics such as velocity of diffusion is fast, and usefulness is lasting, is well suited for being used to regulate indoor humidity.
3, be applied to filtering system, wet curtain paper also has ventilated and corrosion resistance nature, and dirty dirt in the air is had fabulous filteration, is the environment-friendly materials of nonpoisonous and tasteless clean humidification, oxygen supply cooling, so also as purifying air and filtering medium.
The making method of existing wet curtain paper is: body paper is flooded the back hot setting in liquid phenolic resin, utilize the characteristics that deflection is high, water tolerance is strong behind the phenolic resin curing, the performance of wet curtain paper is greatly improved.
At present, wet curtain paper with the synthesis technique of resol generally is: phenol and formaldehyde are under the condition of basic catalyst, and pH is 8～10,70～90 ℃ of isothermal reaction to certain viscosity scopes, promptly obtains desired product.This kind technology is widely used at wet curtain paper, but because the price of phenol is high, about 14000 yuan/ton, causes that production cost is high, rate of profit is low.
Summary of the invention
The present invention is directed to deficiency, propose a kind of wet curtain paper and use resol, adopt low cost raw material to substitute expensive phenol, reduced production cost, and kept product performance.
In order to realize the foregoing invention purpose; The present invention provides following technical scheme: a kind of wet curtain paper uses the preparation method of resol to be: the phenol and the aldehyde that in reaction kettle, add mol ratio 1: 2.0～4.0; And the xylogen and the alkali that accounts for phenol weight 2%～8% that account for phenol weight 10%～60%, carrying out polycondensation, the resin viscosity that extremely generates is 20～50cp/25 ℃; Be cooled to rapidly below 40 ℃, get resol.
Preferably, phenol and the xylogen that accounts for phenol weight 10%～60% are dropped into reaction kettle, refluxed 1.5～2.5 hours, add aldehyde and alkali again.
Preferably, to account for the weight ratio of phenol be 30%～50% to said xylogen.
Preferably, said alkali is sodium hydroxide or Pottasium Hydroxide.
Preferably, the consumption of said alkali is 3%～5% of a phenol weight.
Preferably, said xylogen is alkali lignin, sulfonated lignin, the biomass enzymolysis xylogen that wood pulp or straw pulp produce in the paper industry.
Preferably, said polycondensation is carried out under 70 ℃.
Compared with prior art, the present invention adopts xylogen instead of part phenol, comes novolak resin; Because the reserves of existing xylogen are only second to Mierocrystalline cellulose, and all regenerate every year with 50,000,000,000 tons speed.Pulp and paper industry will be isolated about 1.4 hundred million tons of Mierocrystalline celluloses every year from plant; Obtain the xylogen sub product about 5,000 ten thousand tons simultaneously; But up to now, surpass 95% xylogen still directly enter rivers with " black liquor " or concentrate after burn, seldom be utilized effectively.Preparing method of the present invention has reduced the production cost of resol.Free aldehyde of this patent synthetic resol product and free phenol content are few, and production environment and environment for use are had greatly improved.
Xylogen is a kind of complicated phenol polymer that is formed by four kinds of alcohol monomers (to tonquinol, lubanol, 5-hydroxyl lubanol, sinapyl alcohol).At present xylogen mixes by following three kinds of monomers: the syringyl lignin that is formed by Syringa oblata Lindl. base propane structure monomer polymerization; The guaiacyl xylogen that forms by guaiacyl propane structure monomer polymerization; The p-hydroxybenzene xylogen that forms by p-hydroxybenzene propane structure monomer polymerization.
The chemism of this patent synthetic technology is: in the presence of basic catalyst (pH=8～10), phenol and xylogen are miscible in proportion, add formaldehyde then, and the constant temperature polycondensation forms under the certain temperature.
Resol synthetic ultimate principle is:
(1) in the presence of basic catalyst, phenol and formaldehyde at first react the generation hydroxymethyl phenol, because the influence of methylol makes an ortho position and a contraposition activation on the phenol nuclear.These active hydroxymethyl phenols that when receiving the attack of formaldehyde, generate ortho position or contraposition.
(2) because formaldehyde is excessive, all right and formaldehyde generation addition reaction of hydroxymethyl phenol generates binary methylolphenol and ternary methylolphenol.
(3) product of addition reaction is the mixture of hydroxymethyl phenol and polynary hydroxymethyl phenol, and perhaps reacting each other about these hydroxymethyl phenols and phenol generates the resol of linear structure.
Discover, in the molecular structure of lignin monomer, contain various active functional group simultaneously, wherein hydroxyl exists in xylogen at most, has the physics and the chemical property that how much have directly influenced xylogen of phenolic hydroxyl group with alcoholic extract hydroxyl group and two kinds of forms of phenolic hydroxyl group.Therefore the phenolic hydroxyl group that contains in the xylogen and the structural similitude of resol can replace a part of phenol to react with xylogen.
The present invention also provides a kind of preparation method of wet curtain paper, may further comprise the steps:
1., the phenol and the aldehyde that in reaction kettle, add mol ratio 1: 2.0～4.0; And the xylogen and the alkali that accounts for phenol weight 2%～8% that account for phenol weight 10%～60%, carrying out polycondensation, the resin viscosity that extremely generates is 20～50cp/25 ℃; Be cooled to rapidly below 40 ℃, get resol;
2., with step 1. resol and water by weight 1～2: 3～4 mixings;
3., with step 2. mixing liquid soak into body paper fully, body paper was dried by the fire 10～15 minutes under 60 ℃～70 ℃ conditions; Under 120～130 ℃ of conditions, dried by the fire 30～45 minutes again;
4., the body paper after 3. step dried by the fire is under 40%～50% the condition, to keep 3～4 hours in normal temperature, humidity, obtains wet curtain paper.
Preferably, phenol and the xylogen that accounts for phenol weight 10%～60% are dropped into reaction kettle, stirred 1.5～2.5 hours, add aldehyde and alkali again.
The present invention adopts the almost nil wooden part usually of raw materials cost to replace phenol, and preparation resol re-uses such resol and prepares and to wet curtain paper; Reduced the production cost of wet curtain paper equally; Environmental protection has reduced the environmental pollution of industrial waste xylogen, has improved its utilization ratio.
Embodiment
Describe the present invention below in conjunction with specific embodiment, the description of this part only is exemplary and explanatory, should any restriction not arranged to protection scope of the present invention.
Embodiment 1
Phenol 940 grams (10mol), xylogen 188 grams, 2630 gram concentration are that 37% formaldehyde solution adds the reactor drum mixing; Add sodium hydroxide (content 96%) 37.6 grams; Being warming up to 70 ℃ of constant temperature to resin viscosities is 20～50cp/25 ℃, is cooled to rapidly below 40 ℃, obtains liquid phenolic resin.
Embodiment 2
Phenol 940 grams (10mol), xylogen 376 grams, 2630 gram concentration are that 37% formaldehyde solution adds the reactor drum mixing; Add sodium hydroxide (content 96%) 37.6 grams; Being warming up to 70 ℃ of constant temperature to resin viscosities is 20～50cp/25 ℃, is cooled to rapidly below 40 ℃, obtains liquid phenolic resin.
Embodiment 3
Phenol 940 grams (10mol), xylogen 306 grams, 2710 gram concentration are that 37% formaldehyde solution adds the reactor drum mixing; Add sodium hydroxide (content 96%) 37.6 grams; Being warming up to 60 ℃ of constant temperature to resin viscosities is 20～50cp/25 ℃, is cooled to rapidly below 40 ℃, obtains liquid phenolic resin.
Embodiment 4
Phenol 940 grams (10mol), xylogen 289 grams, 2570 gram concentration are that 37% formaldehyde solution adds the reactor drum mixing; Add Pottasium Hydroxide (content 96%) 37.6 grams; Being warming up to 65 ℃ of constant temperature to resin viscosities is 20～50cp/25 ℃, is cooled to rapidly below 40 ℃, obtains liquid phenolic resin.
Embodiment 5
Phenol 940 grams (10mol), xylogen 3556 grams, 2628 gram concentration are that 37% formaldehyde solution adds the reactor drum mixing; Add sodium hydroxide (content 96%) 37.6 grams; Being warming up to 70 ℃ of constant temperature to resin viscosities is 20～50cp/25 ℃, is cooled to rapidly below 40 ℃, obtains liquid phenolic resin.
Embodiment 6
Phenol 940 grams (10mol), xylogen 376 grams, 2630 gram concentration are that 37% formaldehyde solution adds the reactor drum mixing; Add Pottasium Hydroxide (content 82%) 44.0 grams; Being warming up to 70 ℃ of constant temperature to resin viscosities is 20～50cp/25 ℃, is cooled to rapidly below 40 ℃, obtains liquid phenolic resin.
Embodiment 7
Phenol 940 grams (10mol); Xylogen 376 gram adds reactor drums and mixes, 100 ℃ of back flow reaction 2 hours, and adding 2630 gram concentration is 37% formaldehyde solution; Add sodium hydroxide (content 96%) 37.6 grams; Being warming up to 70 ℃ of constant temperature to resin viscosities is 20～50cp/25 ℃, is cooled to rapidly below 40 ℃, obtains liquid phenolic resin.
The comparative example
Phenol 940 grams (10mol); 1621 gram concentration are that 37% formaldehyde solution adds the reactor drum mixing, add sodium hydroxide (content 96%) 37.6 grams, and being warming up to 70 ℃ of constant temperature to resin viscosities is 20～50cp/25 ℃; Be cooled to rapidly below 40 ℃, obtain liquid phenolic resin.
The method for preparing wet curtain paper with above embodiment synthetic resin:
1) with resol and tap water ratio mixing in 1: 3;
2) body paper is immersed in the resin;
3) paper is placed under 60 ℃ of conditions baking 10 minutes;
4) paper is placed under 130 ℃ of conditions baking 30 minutes;
5) taking-up was put in climatic chamber 3 hours (25 ℃ of temperature and humidity 50%).
The wet curtain paper product that the resol that adopts above embodiment to make is processed carry out performance measurement, measuring method according to: the measuring method GB/T2679.3-1996 of paper and cardboard deflection carries out, result such as following table 1:
The Performance Detection of the wet curtain paper of table 1
| Project | Impregnation resin content % | Deflection (mNm) |
| Embodiment 1 | 16.7 | 5.8 |
| Embodiment 2 | 16.2 | 5.6 |
| Embodiment 3 | 16.4 | 5.7 |
| Embodiment 4 | 16.5 | 5.5 |
| Embodiment 5 | 16.6 | 5.7 |
| Embodiment 6 | 16.3 | 5.5 |
| Embodiment 7 | 16.6 | 5.7 |
| The comparative example | 16.8 | 5.6 |
Wet curtain paper Performance Detection data from last table 1; Can find out that wet curtain paper that the prepared resol of the present invention processes is identical basically with existing conventional resol on impregnation resin content and deflection, that is to say that resol performance that the present invention makes satisfies the request for utilization of existing wet curtain paper.
More than wet curtain paper provided by the present invention has been carried out detailed introduction with the compound method of lignin modification resol, used concrete example among this paper principle of the present invention and embodiment set forth.
The explanation of the foregoing description just is used to help method of the present invention and core concept thereof; One of ordinary skill in the art foundation thought of the present invention, the part that on embodiment and range of application, all can change, in sum, the present disclosure content should not be construed as limitation of the present invention.
Claims (9)
1. a wet curtain paper is with the preparation method of resol; For: in reaction kettle, add phenol and the aldehyde of mol ratio 1 ︰ 2.0～4.0, and the xylogen and the alkali that accounts for phenol weight 2%～8% that account for phenol weight 10%～60%, carry out polycondensation; Resin viscosity to generating is 20～50cp/25 ℃; Be cooled to rapidly below 40 ℃, resol, said xylogen is alkali lignin, sulfonated lignin, the biomass enzymolysis xylogen that wood pulp or straw pulp produce in the paper industry.
2. preparation method as claimed in claim 1 is characterized in that: phenol and the xylogen that accounts for phenol weight 10%～60% are dropped into reaction kettle, refluxed 1.5～2.5 hours, add aldehyde and alkali again.
3. according to claim 1 or claim 2 preparation method, it is characterized in that: the weight ratio that said xylogen accounts for phenol is 30%～50%.
4. according to claim 1 or claim 2 preparation method, it is characterized in that: said alkali is sodium hydroxide or Pottasium Hydroxide.
5. preparation method as claimed in claim 3 is characterized in that: the consumption of said alkali is 3%～5% of a phenol weight.
6. preparation method as claimed in claim 1 is characterized in that: said polycondensation is carried out under 70 ℃.
7. resol of making of preparation method according to claim 1.
8. the preparation method of a wet curtain paper may further comprise the steps:
1., the phenol and the aldehyde that in reaction kettle, add mol ratio 1 ︰ 2.0～4.0; And the xylogen and the alkali that accounts for phenol weight 2%～8% that account for phenol weight 10%～60%, carrying out polycondensation, the resin viscosity that extremely generates is 20～50cp/25 ℃; Be cooled to rapidly below 40 ℃, get resol;
2., with step 1. resol and water by weight 1～2 ︰, 3～4 mixings;
3., with step 2. mixing liquid soak into body paper fully, body paper was dried by the fire 10～15 minutes under 60 ℃～70 ℃ conditions; Under 120～130 ℃ of conditions, dried by the fire 30～45 minutes again;
4., the body paper after 3. step dried by the fire is under 40%～50% the condition, to keep 3～4 hours in normal temperature, humidity, obtains wet curtain paper.
9. preparation method as claimed in claim 8 is characterized in that: phenol and the xylogen that accounts for phenol weight 10%～60% are dropped into reaction kettle, stirred 1.5～2.5 hours, add aldehyde and alkali again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110074525A CN102174159B (en) | 2011-03-25 | 2011-03-25 | Phenol-formaldehyde resin for wet curtain paper and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110074525A CN102174159B (en) | 2011-03-25 | 2011-03-25 | Phenol-formaldehyde resin for wet curtain paper and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102174159A CN102174159A (en) | 2011-09-07 |
| CN102174159B true CN102174159B (en) | 2012-10-17 |
Family
ID=44517434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110074525A Active CN102174159B (en) | 2011-03-25 | 2011-03-25 | Phenol-formaldehyde resin for wet curtain paper and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102174159B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432789A (en) * | 2011-09-29 | 2012-05-02 | 山东圣泉化工股份有限公司 | Phenolic resin for wet curtain paper, preparation method of phenolic resin and preparation method of wet curtain paper |
| US9328188B2 (en) | 2011-12-29 | 2016-05-03 | Industrial Technology Research Institute | Method for preparing phenol-formaldehyde resins, resin materials and method for preparing resin molding materials |
| TW201326268A (en) * | 2011-12-29 | 2013-07-01 | Ind Tech Res Inst | Method for preparing phenol-formaldehyde resins from biomass pyrolysis oil and resin materials prepared from the phenol-formaldehyde resins |
| CN102604322B (en) * | 2012-02-15 | 2014-01-15 | 山东圣泉化工股份有限公司 | Phenolic resin compound for wet-curtain paper, preparation method of phenolic resin compound and preparation method of wet-curtain paper |
| CN102604323B (en) * | 2012-02-22 | 2013-07-17 | 太尔胶粘剂(广东)有限公司 | Phenol-formaldehyde resin for wet curtain paper and preparation method |
| CN102718935B (en) * | 2012-07-09 | 2014-08-13 | 山东圣泉化工股份有限公司 | Preparation method of phenolic resin for wet curtain paper and preparation method of wet curtain paper |
| DE102013008687A1 (en) | 2013-05-22 | 2014-11-27 | Stefan Martin Hanstein | Production of aqueous reaction solutions based on vegetable hydroxycinnamic acids (phenolic acids / phenylpropanoids / phenylpropenes) and lignin for the coating of fertilizer granules. In particular: preparation of appropriate reaction solutions |
| CN104087217B (en) * | 2014-06-25 | 2015-09-16 | 中国林业科学研究院林产化学工业研究所 | The preparation method of a kind of straw ethanol by product methylolation and composite wood sizing agent |
| CN104294701A (en) * | 2014-09-23 | 2015-01-21 | 北京纳迅科技有限公司 | Phenolic resin solution for paper wet curtain and paper wet curtain |
| CN106810656B (en) * | 2016-12-29 | 2019-05-21 | 广西玉林利而安化工有限公司 | A kind of phenol-formaldehyde resin modified and preparation method thereof |
| CN111285984A (en) * | 2020-03-02 | 2020-06-16 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin-based water-soluble phenolic resin |
| CN114561189B (en) * | 2022-03-23 | 2023-06-02 | 南京工业大学 | Lignin phenolic resin dust suppressant and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB529628A (en) * | 1938-06-04 | 1940-11-25 | British Thomson Houston Co Ltd | Improvements in and relating to synthetic resinous compositions and methods of making the same |
| CN101067016A (en) * | 2007-05-21 | 2007-11-07 | 张一帆 | Synthesis and usage of fast curing phenolic resin |
| CN101942068B (en) * | 2010-08-27 | 2012-09-05 | 安徽格义清洁能源技术有限公司 | Preparation method of lignin phenolic resin |
-
2011
- 2011-03-25 CN CN201110074525A patent/CN102174159B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102174159A (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102174159B (en) | Phenol-formaldehyde resin for wet curtain paper and method for preparing same | |
| CN102432789A (en) | Phenolic resin for wet curtain paper, preparation method of phenolic resin and preparation method of wet curtain paper | |
| Yang et al. | Lignin–phenol–formaldehyde resin adhesives prepared with biorefinery technical lignins | |
| CN102718935B (en) | Preparation method of phenolic resin for wet curtain paper and preparation method of wet curtain paper | |
| CN103319673B (en) | Modification method of melamine formaldehyde resin | |
| CN104004479A (en) | Phenolate lignin tackiness agent and preparing method of phenolate lignin tackiness agent | |
| CN101260283B (en) | Method for preparing phenolic aldehyde adhesive based on lignin phenolized liquid and application thereof | |
| CN101348698B (en) | Preparation of alkali lignin-phenolic composite adhesive for timber industry | |
| CN103804618B (en) | A kind of preparation method of lignin-base Environmental protection phenol formaldehyde resin sizing agent | |
| CN104087217B (en) | The preparation method of a kind of straw ethanol by product methylolation and composite wood sizing agent | |
| CN102120810B (en) | Preparation method of high solid content expandable melamine modified urea resin | |
| CN101269930A (en) | Enzymolysis xylogen or its derivative modified pnenolic aldehyde foam material and preparation method thereof | |
| CN105348465A (en) | Preparation method of E0-grade melamine modified urea formaldehyde resin | |
| CN103555237A (en) | Method for preparing environment-friendly adhesive for biomass wood materials | |
| CN103145938A (en) | Lignin-modified phenolic resin and synthetic method thereof as well as grinding wheel comprising lignin-modified phenolic resin | |
| CN102408673B (en) | Epoxidized soybean oil modified phenolic resin and method for producing non-fire-retardant paper based copper clad laminate by using same | |
| CN113831490A (en) | High-strength water-based phenolic resin and preparation method thereof | |
| Sarika et al. | Progress in Bio‐Based Phenolic Foams: Synthesis, Properties, and Applications | |
| CN103554400A (en) | Liquefaction method of lignin for preparing thermoplastic phenolic resin | |
| CN100497422C (en) | Lignin modified phenol furfural resin for moulding material and preparation method thereof | |
| US9328188B2 (en) | Method for preparing phenol-formaldehyde resins, resin materials and method for preparing resin molding materials | |
| US20130172451A1 (en) | Method for preparing phenol-formaldehyde resins, resin materials and method for preparing resin molding materials | |
| CN109251471A (en) | Tricresyl phosphate cashew nut phenolic ester plasticized modifier and preparation method and applications | |
| Xu et al. | Lignin-based phenol–formaldehyde (LPF) resins/adhesives | |
| CN103666606A (en) | Lignin water coal slurry additive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Phenol-formaldehyde resin for wet curtain paper and method for preparing same Effective date of registration: 20160302 Granted publication date: 20121017 Pledgee: Industrial Commercial Bank of China Ltd Zhangqiu branch Pledgor: Shengquan Group Co., Ltd., Ji'nan City Registration number: 2016990000130 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20190709 Granted publication date: 20121017 Pledgee: Industrial Commercial Bank of China Ltd Zhangqiu branch Pledgor: Shengquan Group Co., Ltd., Ji'nan City Registration number: 2016990000130 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |