CN103467682A - Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method - Google Patents
Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method Download PDFInfo
- Publication number
- CN103467682A CN103467682A CN2013103656662A CN201310365666A CN103467682A CN 103467682 A CN103467682 A CN 103467682A CN 2013103656662 A CN2013103656662 A CN 2013103656662A CN 201310365666 A CN201310365666 A CN 201310365666A CN 103467682 A CN103467682 A CN 103467682A
- Authority
- CN
- China
- Prior art keywords
- barium sulfate
- phenol
- polycondensation
- water
- add
- 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.)
- Granted
Links
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 7
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 7
- 229920001568 phenolic resin Polymers 0.000 title abstract description 5
- 238000001556 precipitation Methods 0.000 title abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract 3
- 239000005011 phenolic resin Substances 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 5
- 239000000057 synthetic resin Substances 0.000 claims abstract description 5
- -1 phenol, solid aldehyde Chemical class 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 30
- 229920003987 resole Polymers 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 8
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 8
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 8
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 8
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 235000013824 polyphenols Nutrition 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 206010033307 Overweight Diseases 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000020825 overweight Nutrition 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 239000002351 wastewater Substances 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 abstract description 6
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 abstract 2
- 229910001863 barium hydroxide Inorganic materials 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 6
- 238000007664 blowing Methods 0.000 description 4
- 239000002783 friction material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a process for circularly producing thermoplastic barium sulfate phenolic resin by a precipitation method. The process comprises the following steps: according to a formula of synthetic resin, adding phenol, solid aldehyde and water into a reaction kettle with a cooler and a stirrer, heating to a temperature of 50 to 80 DEG C, depolymerizing and adding sulfuric acid to perform the catalytic reaction until a sampled sample is not sticky and is slightly hard in water with a temperature of 20 DEG C; cooling a reaction material to a temperature of 95 to 96 DEG C and adding barium hydroxide with stirring to stop the catalytic reaction; neutralizing the sulfuric acid by the barium hydroxide to generate water and barium sulfate precipitates, enabling the pH value of the reaction material to be 7, firstly carrying out normal pressure processing and then carrying out vacuum dehydration to obtain the semitransparent solid thermoplastic barium sulfate phenolic resin product and a polycondensation dehydration fraction; reusing the polycondensation dehydration fraction into the reaction kettle to carry out circular production. The process has zero discharge of wastewater, is beneficial to the environment protection, is suitable for industrial production and has good economic benefits.
Description
Technical field
The invention belongs to the synthetic field of resol, be specifically related to a kind of technique of precipitator method cyclic production thermoplasticity barium sulfate resol, can accomplish that wastewater zero discharge, raw material phenol utilization ratio almost reach 100%.
Background technology
The novolac resin product is mainly used in the industries such as bonding wood materials processing, moulding compound, insulating material, heat-insulating and sound-proof material, friction material section, coating, printing ink, oil field, paint, rubber, and wherein the resol through modification is being widely used in military affairs, Aeronautics and Astronautics and other sophisticated technology field as high-temperature-resistant adhesive and body material.
The novolac resin traditional mode of production adopts phenol and formalin to form through polycondensation under an acidic catalyst.Take that to have friction materials novolac resin production method commonly used now be example, production method is as follows: with water cooler, add phenol in the reactor of agitator, formaldehyde (37%) aqueous solution, 1/3rd of hydrochloric acid, being heated to 70～80 ℃ utilizes reaction heat to be warmed up to material backflow is arranged, slowly add residue hydrochloric acid after material reaction is mild, react sampling after 60 minutes, sample is tack-free in 20 ℃ of water is reaction end, add 1/2nd the water of 50～60 ℃ of amount of resin to be washed, stop stirring after a moment, vacuum sucked upper water liquid and wash for the second time, add again 1/2nd the water of 50～60 ℃ of amount of resin to be washed, stop stirring after a moment, vacuum sucked upper water liquid and dewatered, it is that the 80KPa material temperature is the dehydration reaction terminal while being 125 ℃ that first normal pressure final vacuum is dewatered to pressure, blowing is cooling to charging tray, obtain transparent solid novolac resin and polycondensation dehydrated fraction.
There is following drawback in aforesaid method: can produce a large amount of waste water in (1) washing process production process, one ton of resol of every production produces two tons of waste water, contains the derivative of hydrochloric acid, free phenol, loss resin and phenol in waste water, and administers containing Cl
--, the phenolic wastewater difficulty is high, expense is large, need to drop into a large amount of manpower, equipment and fund, regulation effect also is difficult to reach people's will, will cause great pollution to environment.(2) washing process can not stop catalyzed reaction, a slowed down reaction speed fully.During washing, resin easily runs off, and the resin run off can only be made the small molecules amount resin that price is lower when wastewater treatment.(3) a small amount of Cl that resin contains
--ion can affect product to be preserved, and easily makes the resin variable color.
Because novolac resin tradition washing process raw material availability is low, the unit output production cost is high, yield is low, waste is large, preservation period is short, large, the waste water treatment occupation of land of power consumption, water consumption greatly, defect that cost is high, seriously hindered the development of phenolic aldehyde industry.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect existed in prior art, a kind of technique of precipitator method cyclic production thermoplasticity barium sulfate resol is provided, can do wastewater zero discharge, raw material phenol utilization ratio almost reaches 100%.
The technique of precipitator method cyclic production thermoplasticity barium sulfate resol, is characterized in that, comprises the following steps:
(a) according to the synthetic resins formula, add phenol, solid aldehyde and water in the reactor with water cooler, agitator, be heated to 50～80 ℃ of depolymerization after vulcanization acid catalyzed reactions tack-free micro-hard in 20 ℃ of water to the sampling sample;
(b) cooling reaction mass to 95～96 ℃, under agitation add hydrated barta to stop catalyzed reaction, and the hydrated barta neutralisation of sulphuric acid, generate water and barium sulfate precipitate, and making reaction mass pH value is 7;
(c) first normal pressure again vacuum hydro-extraction obtain translucent solid thermoplastic barium sulfate resol product and polycondensation dehydrated fraction; Wherein, the weight percent 1～3% of barium sulfate in the resol product; Contain the free phenol of 2000～5000mg/l, free formaldehyde, loss resin and organic low molecular compounds and the micro-barium sulfate of 1000～3000mg/l in the polycondensation dehydrated fraction;
(d) reuse of polycondensation dehydrated fraction is to the described reactor of step (a), cyclic production.
Further, the phenol described in step (a) is phenol or phenol and polyphenol, or phenol and cardanol; Described aldehyde is formaldehyde, acetaldehyde or furfural, can also be other aldehydes.The add-on of water etc. overweights the weight of phenol, the add-on of sulfuric acid is 0.2～2% of the gross weight that feeds intake.
In step (b), the add-on of hydrated barta is equivalent sulfuric acid.
In step (d), the concrete steps of polycondensation dehydrated fraction reuse are: add phenol, solid formaldehyde, polycondensation dehydrated fraction according to the synthetic resins formula, the add-on of polycondensation dehydrated fraction is with the gross weight 1:1 of phenol～1.2; Then repeating step (b)-(d).
The reaction formula of phenol-formaldehyde reaction is as follows:
The reaction formula that the hydrated barta neutralisation of sulphuric acid generates water and barium sulfate precipitate is:
H
2SO
4+Ba(OH)
2=BaSO
4↓+H
2O。
With sulfuric acid (H
2sO
4) as the phenol-formaldehyde reaction catalyzer, with hydrated barta (Ba (OH)
2* 8H
2o) be the method for reaction terminating agent, can control well reaction end, guarantee thermoplasticity barium sulfate resol steady quality, and resin is easily preserved.Thermoplasticity barium sulfate resol output capacity is high, and in resin, free phenol content is low, and free phenol in the polycondensation dehydrated fraction, free formaldehyde content are low, the component substantially constant, and cut adds corresponding formula recycle not affect the resin formula component structure.And avoided adding the hydrochloric acid that affects the subsequent product quality index in the material of reaction, for condition has been created in the recycle of polycondensation dehydrated fraction; Barium sulfate (BaSO4) precipitation generated can be improved high-temperature behavior, the raising cohesive strength of resin; Barium sulfate can reduce the hardness of friction materials, improves shock strength, reduces wear rate, 350 ℃ of high temperature, can control preferably the fluctuation of rubbing factor with temperature.
The thermoplasticity barium sulfate resol product moisture 1～4% that utilizes the inventive method to make, building-up process produces the water of reducible resin finished product 9%, under 100～150 ℃ of high temperature, 0～80KPa vacuum, in underpressure distillation when dehydration, have little time coolingly to cause part steam, low molecule to enter vacuum system and 3～10% water and low molecule of loss resin finished product, therefore may need to add part water during the recycle cut.
Beneficial effect of the present invention:
(1) thermoplasticity barium sulfate resol does not wash with water, has reduced energy consumption, labour cost, has saved water rate, has avoided the generation of waste water.
(2) recycle of cut makes the utilization rate of raw materials such as phenol almost reach 100%, has saved expensive waste water treatment expense simultaneously, has really reached cyclic production, and wastewater zero discharge, be conducive to environment protection.
(3) in novolac resin, add barium sulfate can improve high-temperature behavior, cohesive strength; Barium sulfate can reduce the hardness of friction materials, improves shock strength, reduces wear rate.Each index controlled range of thermoplasticity barium sulfate resol product is as following table.
Barium sulfate resol product quality controlled range
| Sequence number | Project | Index |
| 1 | Gelation time | 20—100S/150℃ |
| 2 | Softening temperature | 75—120℃ |
| 3 | Degree of mobilization | 10—70MM |
| 4 | Free phenol | ≤4% |
| 5 | Moisture content | 1—4% |
The inventive method is applicable to suitability for industrialized production, has good economic benefit.
Embodiment
Embodiment 1: preparation thermoplasticity barium sulfate resol
Preparation thermoplasticity barium sulfate resol formula can be following scope:
Start 1000 liters of stirrings with condenser, agitator, fast opening, jacket steam heating and water-cooled reactor, add phenol 250Kg, solid formaldehyde 65Kg, polycondensation dehydrated fraction or deionized water 250Kg, open and be steam heated to 50～80 ℃ by after the formaldehyde depolymerization, slowly add sulfuric acid (50%) 1Kg, be warmed up to backflow carefully, after after question response is mild, a minute secondary slowly adds residual sulfuric acid (50%) 2Kg, backflow samples in 1 hour, sample in 20 ℃ of water tack-free when harder chuck to be cooled to material temperature be 96 ℃, slowly add hydrated barta (Ba (OH)
2* 8H
2o) 4.8Kg neutralisation of sulphuric acid, termination catalyzed reaction, generate barium sulfate precipitate and water, then the normal pressure that heats up carries out vacuum hydro-extraction while being dewatered to 110 ℃ of material temperatures, when pressure is that the 80KPa material temperature is reaction end while being 126 ℃, blowing is cooling to charging tray, obtains translucent solid thermoplastic barium sulfate resol and polycondensation dehydrated fraction; The polycondensation dehydrated fraction is extracted in the cut storage tank standby by vacuum, feeds intake and carry out the production of next still by this technical recipe, with this cyclic production, wastewater zero discharge.
Embodiment 2: the preparation of low cardanol thermoplasticity barium sulfate resol
Formula can be following scope:
Start 1000 liters of stirrings with condenser, agitator, fast opening, jacket steam heating and water-cooled reactor, add phenol 345Kg, solid formaldehyde 91Kg, cardanol 59Kg, polycondensation dehydrated fraction 345Kg, open and be steam heated to 50～80 ℃ by after the formaldehyde depolymerization, slowly add sulfuric acid (50%) 2.3Kg, be warmed up to backflow carefully, after after question response is mild, a minute secondary slowly adds residual sulfuric acid (50%) 5.4.Kg, backflow samples in 1 hour, sample in 20 ℃ of water tack-free when harder chuck to be cooled to material temperature be 95-96 ℃, slowly add hydrated barta (Ba (OH)
2* 8H
2o) 12.4Kg neutralisation of sulphuric acid, termination catalyzed reaction, generate barium sulfate precipitate and water, then the normal pressure that heats up carries out vacuum hydro-extraction while being dewatered to 110 ℃ of material temperatures, when pressure is that the 80KPa material temperature is reaction end while being 138 ℃, blowing is cooling to charging tray, must hang down cardanol solid thermoplastic barium sulfate resol and polycondensation dehydrated fraction; The polycondensation dehydrated fraction is extracted in the cut storage tank standby by vacuum, feeds intake and carry out the production of next still by this technical recipe, with this cyclic production, wastewater zero discharge.
The preparation of the high cardanol thermoplasticity of embodiment 3. barium sulfate resol
Formula can be following scope:
Start 1000 liters of stirrings with condenser, agitator, fast opening, jacket steam heating and water-cooled reactor, add phenol 220Kg, solid formaldehyde 65Kg, cardanol 72Kg, polycondensation dehydrated fraction and deionized water 220Kg, open and be steam heated to 50～80 ℃ by after the formaldehyde depolymerization, slowly add sulfuric acid (50%) 2Kg, be warmed up to backflow carefully, after after question response is mild, a minute secondary slowly adds residual sulfuric acid (50%) 6Kg, backflow samples in 1 hour, sample in 20 ℃ of water tack-free when harder chuck to be cooled to material temperature be 96 ℃, slowly add hydrated barta (Ba (OH)
2* 8H
2o) 4.8Kg neutralisation of sulphuric acid, termination catalyzed reaction, generate barium sulfate precipitate and water, then the normal pressure that heats up carries out vacuum hydro-extraction while being dewatered to 110 ℃ of material temperatures, when pressure is that the 80KPa material temperature is reaction end while being 138 ℃, blowing is cooling to charging tray, obtains the high cardanol thermoplasticity of solid barium sulfate resol and polycondensation dehydrated fraction; The polycondensation dehydrated fraction is extracted in the cut storage tank standby by vacuum, feeds intake and carry out the production of next still by this technical recipe, with this cyclic production, wastewater zero discharge.
Claims (6)
1. the technique of precipitator method cyclic production thermoplasticity barium sulfate resol, is characterized in that, comprises the following steps:
(a) according to the synthetic resins formula, add phenol, solid aldehyde and water in the reactor with water cooler, agitator, be heated to 50～80 ℃ of depolymerization after vulcanization acid catalyzed reactions tack-free micro-hard in 20 ℃ of water to the sampling sample;
(b) cooling reaction mass to 95～96 ℃, under agitation add hydrated barta to stop catalyzed reaction, and the hydrated barta neutralisation of sulphuric acid, generate water and barium sulfate precipitate, and making reaction mass pH value is 7;
(c) first normal pressure again vacuum hydro-extraction obtain translucent solid thermoplastic barium sulfate resol product and polycondensation dehydrated fraction; Wherein, the weight percent 1～3% of barium sulfate in the resol product; Contain the free phenol of 2000～5000mg/l, free formaldehyde, loss resin and organic low molecular compounds and the micro-barium sulfate of 1000～3000mg/l in the polycondensation dehydrated fraction;
(d) reuse of polycondensation dehydrated fraction is to the described reactor of step (a), cyclic production.
2. technique according to claim 1, is characterized in that, in step (a), described phenol is phenol or phenol and polyphenol, or phenol and cardanol.
3. technique according to claim 1, is characterized in that, in step (a), described aldehyde is formaldehyde, acetaldehyde or furfural.
4. technique according to claim 1, is characterized in that, in step (a), the add-on of water etc. overweights the weight of phenol, the add-on of sulfuric acid is 0.2～2% of the gross weight that feeds intake.
5. technique according to claim 1, is characterized in that, in step (b), the add-on of hydrated barta is equivalent sulfuric acid.
6. technique according to claim 1, it is characterized in that, in step (d), the concrete steps of polycondensation dehydrated fraction reuse are: add phenol, solid formaldehyde, polycondensation dehydrated fraction according to the synthetic resins formula, the add-on of polycondensation dehydrated fraction is with the gross weight 1:1 of phenol～1.2; Then repeating step (b)-(d).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310365666.2A CN103467682B (en) | 2013-08-20 | 2013-08-20 | Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310365666.2A CN103467682B (en) | 2013-08-20 | 2013-08-20 | Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103467682A true CN103467682A (en) | 2013-12-25 |
| CN103467682B CN103467682B (en) | 2015-05-13 |
Family
ID=49792740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310365666.2A Active CN103467682B (en) | 2013-08-20 | 2013-08-20 | Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467682B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315418A (en) * | 2015-11-14 | 2016-02-10 | 浙江越拓新材料科技有限公司 | Tungsten disulfide modified phenolic resin and preparation method thereof |
| CN107987237A (en) * | 2017-12-12 | 2018-05-04 | 济南鲁东耐火材料有限公司 | A kind of preparation method of phenolic resin for refractory material |
| CN113234202A (en) * | 2021-06-15 | 2021-08-10 | 河北泽田化工有限公司 | High-moisture-retention phenolic resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121811A (en) * | 2007-10-09 | 2008-02-13 | 上海安亿纳米材料有限公司 | Modified phenolic resin and its preparing process |
| CN102002139A (en) * | 2010-10-22 | 2011-04-06 | 兰州石化职业技术学院 | Method for preparing modified phenolic resin for coating with cresol residue |
| CN103059237A (en) * | 2012-12-12 | 2013-04-24 | 江苏锋芒复合材料科技集团有限公司 | Wastewater zero discharge preparing method of thermoplastic phenolic resin |
-
2013
- 2013-08-20 CN CN201310365666.2A patent/CN103467682B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121811A (en) * | 2007-10-09 | 2008-02-13 | 上海安亿纳米材料有限公司 | Modified phenolic resin and its preparing process |
| CN102002139A (en) * | 2010-10-22 | 2011-04-06 | 兰州石化职业技术学院 | Method for preparing modified phenolic resin for coating with cresol residue |
| CN103059237A (en) * | 2012-12-12 | 2013-04-24 | 江苏锋芒复合材料科技集团有限公司 | Wastewater zero discharge preparing method of thermoplastic phenolic resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315418A (en) * | 2015-11-14 | 2016-02-10 | 浙江越拓新材料科技有限公司 | Tungsten disulfide modified phenolic resin and preparation method thereof |
| CN105315418B (en) * | 2015-11-14 | 2019-02-05 | 浙江越拓新材料科技有限公司 | Tungsten disulfide phenol-formaldehyde resin modified and preparation method thereof |
| CN107987237A (en) * | 2017-12-12 | 2018-05-04 | 济南鲁东耐火材料有限公司 | A kind of preparation method of phenolic resin for refractory material |
| CN113234202A (en) * | 2021-06-15 | 2021-08-10 | 河北泽田化工有限公司 | High-moisture-retention phenolic resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103467682B (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101143917A (en) | Cashew shell modified alkyd resin and preparation method thereof | |
| CN101906196A (en) | Comprehensive utilization method of phenolic resin wastewater | |
| CN104693679A (en) | Preparation method of nano-silica rosin modified phenolic resin | |
| CN103467682B (en) | Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method | |
| CN103145939A (en) | Modification method of xylene formaldehyde resin | |
| CN102219883A (en) | Production method of solid-thermosetting phenolic resin | |
| CN102108115B (en) | Phenolic resin for environment-friendly thermoplastic refractory material and preparation method thereof | |
| CN104293258B (en) | Method for recycling papermaking waste liquid and adhesive produced by same | |
| CN115785394A (en) | Modified o-cresol formaldehyde epoxy resin and preparation method thereof | |
| CN113801431B (en) | High-toughness high-strength phenolic resin material and preparation method thereof | |
| CN112358589B (en) | Method for preparing high-bonding-strength phenolic resin by resource utilization of dai seek byproduct | |
| CN101418066B (en) | A kind of urea-isobutyraldehyde-formaldehyde resin continuous production process | |
| CN101343256A (en) | Preparation method for rubber accelerator CBS | |
| CN114736488B (en) | A kind of preparation method of high compressive and refractory composite epoxy foam | |
| CN107778491A (en) | A kind of preparation method of 3D printing furane resins | |
| CN103319670B (en) | Bio-based phenolic resin and preparation method thereof | |
| CN110918868B (en) | Ester-cured phenolic resin for large-scale casting and molding and preparation method thereof | |
| CN103467685A (en) | Phosphorus modified phenolic resin and preparation method thereof | |
| CN115636914A (en) | Reinforced resin for tire rubber and preparation method and application thereof | |
| CN103450426A (en) | Phosphorus-modified phenolic resin and preparation method thereof | |
| CN110655627A (en) | Waste water treatment method in furfuryl alcohol production process | |
| CN117801312A (en) | Inorganic modified lignin and preparation method and application thereof | |
| CN103450427A (en) | Phosphorus-modified phenolic resin and preparation method thereof | |
| CN103450429A (en) | Phosphorus-modified phenolic resin and preparation method thereof | |
| CN118005908A (en) | Epoxy resin glass polymer 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 |