CN110092878A - The preparation method of aqueous rock wool glue phenolic resin - Google Patents
The preparation method of aqueous rock wool glue phenolic resin Download PDFInfo
- Publication number
- CN110092878A CN110092878A CN201910371885.9A CN201910371885A CN110092878A CN 110092878 A CN110092878 A CN 110092878A CN 201910371885 A CN201910371885 A CN 201910371885A CN 110092878 A CN110092878 A CN 110092878A
- Authority
- CN
- China
- Prior art keywords
- preparation
- formalin
- phenolic resin
- catalyst
- added
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/08—Ureas; Thioureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
Abstract
The invention discloses a kind of preparation methods of aqueous rock wool glue phenolic resin, belong to chemical field.Method includes the following steps: under conditions of catalyst condensation reaction occurs for A, phenol and formalin, pure phenolic resin initial material is obtained, formalin and catalyst are added in two portions, and add phenol and catalyst in the reactor first, heating melting is at liquid；The formalin of volume is added for the first time, increases temperature to 50-60 DEG C, is stirred to react 90-180min；Secondary addition catalyst increases temperature to 65-70 DEG C, continues to be stirred to react 30-120min；It is eventually adding remaining formalin, increases temperature to 80-90 DEG C, constant temperature continues to be stirred to react 30-60min；B, modifying agent and diluent are added into the pure phenolic resin initial material that step A is obtained, obtains aqueous rock wool glue phenolic resin.Preparation method of the present invention is easy to operate, energy saving, reduces cost, more environmentally friendly.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of preparation method of aqueous rock wool glue phenolic resin.
Background technique
Phenolic resin react under the conditions of being phenols and aldehydes existing for the catalyst generation resin general designation, be most
The early high molecular material for realizing industrialized production, with good dimensional stability, flame retardant property, acid resistance, mechanical property
Energy and heat resistance are widely used in the industries such as steel, automobile, machining, electronic apparatus, aerospace, heat-insulating neck
Domain.Asbestos product is a kind of New Building Materials, is widely used in interior decoration and exterior-wall heat insulation.Resol resins auxiliary is added
A certain amount of additive is the primary bond material for producing asbestos product.Usually there is curing time in existing resol resins
Long, the disadvantages of storage stability is bad, storage time is short, resin is perishable, higher cost, exceeded free phenolic aldehyde burst size, from
And causing rock wool properties of product unstable, product quality defect is big, and the use of phenolic resin is made also to receive certain limitation.
Researcher once used many methods to the mechanical property of aqueous phenolic aldehyde adhesive, curing performance, shelf characteric and
Environmental-protecting performance etc. is modified research, wherein the gluing that can effectively improve phenolic resin is added as modifying agent using urea
Intensity, curing rate, the performances such as storage stability reduce its solidification temperature, reduce free formaldehyde release etc..
Prior art discloses a variety of methods using urea modified phenolic resin, such as make urea, phenol and formaldehyde one
Determine three under synthesis condition to be copolymerized；Or phenol is first reacted with formaldehyde, when carrying out to a certain extent wait react, is added
Urea, then polymerize generation urea-phenol-formaldehyde copolymer resins etc..But above-mentioned modified preparation process is relatively complicated, is not easy
Control the extent of reaction of three.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of the aqueous rock wool glue phenolic resin of letter section.
Technical solution of the present invention is as follows: a kind of preparation method of aqueous rock wool glue phenolic resin, comprising the following steps:
A, under conditions of catalyst condensation reaction occurs for phenol and formalin, obtains pure phenolic resin initial material, formalin
It is added in two portions with catalyst,
Add phenol and catalyst in the reactor first, heating melting is at liquid；The formalin of volume is added for the first time, increases
Temperature is stirred to react 90-180min to 50-60 DEG C；Secondary addition catalyst increases temperature to 65-70 DEG C, continues to be stirred to react
30-120min；It is eventually adding remaining formalin, increases temperature to 80-90 DEG C, constant temperature continues to be stirred to react 30-60min；
B, modifying agent and diluent are added into the pure phenolic resin initial material that step A is obtained, obtains aqueous rock wool glue with phenolic aldehyde tree
Rouge.
As a further improvement of the present invention, phenol and the mass ratio of formalin are 1:1.7-2.6 in the step A.
As a further improvement of the present invention, in the step A catalyst and phenol and formaldehyde pure material total amount quality
Than for 0.03-0.05:1.
As a further improvement of the present invention, the first time additional amount of formalin is 80% in the step A, and formaldehyde is molten
The concentration of liquid is 37%.
As a further improvement of the present invention, the first time additional amount of catalyst is 66-68.6% in the step A.
As a further improvement of the present invention, catalyst is sodium hydroxide, barium hydroxide, ammonium hydroxide, chlorination in the step A
One or both of ammonium.
As a further improvement of the present invention, the addition manner of modifying agent and diluent is at 10-20 DEG C in the step B
Lower constant temperature stirring, mixing time 20-30min.
As a further improvement of the present invention, modifying agent and the mass ratio of pure phenolic resin initial material are in the step B
0.1-0.2:1。
As a further improvement of the present invention, modifying agent is urea in the step B.
As a further improvement of the present invention, diluent is water in the step B.
Compared with prior art, the present invention with phenol and excess formaldehyde solution (37%) for raw material, in 50-90 DEG C of range and
It is reacted under conditions of catalyst, obtains pure phenolic resin initial material；Then into the pure phenolic resin initial material be added modifying agent and
Diluent, it is only necessary to aqueous rock wool glue phenolic resin is obtained after mixing evenly under normal temperature conditions, is reacted without heating, it is special
Point is:
A. the modifying agent described in the asbestos product hot setting stage may participate in reaction, and the secondary of free formaldehyde solution is caught in realization
It catches, Lauxite is generated under high temperature can further strengthen its adhesiveness, improve the performance of asbestos product；
B. the aqueous rock wool glue under traditional preparation methods is just able to achieve effective solidification at 180 DEG C with synvaren, and originally
Resin glue under preparation method can be achieved with solidifying at 150 DEG C, and solidification at a lower temperature can be between rock wool fibers
Cohesive force and uniformity provide effective guarantee.
C. preparation method of the present invention is easy to operate compared with traditional preparation methods, energy saving, reduces cost, more ring
It protects.
Specific embodiment
In order to further illustrate the present invention, with reference to embodiments to aqueous rock wool glue phenolic resin provided by the invention
And preparation method thereof be described in detail.
Embodiment 1
A. 100g phenol is added in the reactor, 5.4g sodium hydroxide, heating melting is at liquid；140g formalin is added
(37%), temperature is increased to 50 DEG C, is stirred to react 90min；2.7g sodium hydroxide is added, temperature is increased to 65 DEG C, continues to stir
React 30min；It is eventually adding remaining 30g formalin (37%), increases temperature to 80 DEG C, constant temperature continues to be stirred to react 30min.
Cooling discharge obtains pure phenolic resin initial material rapidly after sampling viscosimetric is qualified.
B. 10g urea and 35g water is added in the pure phenolic resin initial material for taking 100g step A to obtain, and constant temperature stirs at 10 DEG C
20min obtains aqueous rock wool glue phenolic resin.
Embodiment 2
A. 100g phenol is added in the reactor, 8g barium hydroxide, heating melting is at liquid；It is added 160g formalin (37%),
Temperature is increased to 55 DEG C, is stirred to react 120min；4g barium hydroxide is added, temperature is increased to 70 DEG C, continues to be stirred to react
60min；It is eventually adding remaining 40g formalin (37%), increases temperature to 86 DEG C, constant temperature continues to be stirred to react 60min.Sampling
Cooling discharge obtains pure phenolic resin initial material rapidly after viscosimetric is qualified.
B. 15g urea and 40g water is added in the pure phenolic resin initial material for taking 100g step A to obtain, and constant temperature stirs at 15 DEG C
30min obtains aqueous rock wool glue phenolic resin.
Embodiment 3
A. 100g phenol is added in the reactor, 12g ammonium hydroxide, heating melting is at liquid；It is added 210g formalin (37%), rises
High-temperature is stirred to react 180min to 60 DEG C；6g ammonium hydroxide is added, temperature is increased to 70 DEG C, continues to be stirred to react 120min；Most
Residue 50g formalin (37%) is added afterwards, increases temperature to 90 DEG C, constant temperature continues to be stirred to react 60min.Viscosimetric is sampled to close
Rapid cooling discharge obtains pure phenolic resin initial material after lattice.
B. 20g urea and 45g water is added in the pure phenolic resin initial material for taking 100g step A to obtain, and constant temperature stirs at 20 DEG C
30min obtains aqueous rock wool glue phenolic resin.
Embodiment 4
A. 100g phenol, 5.5g sodium hydroxide and 0.4g ammonium chloride are added in the reactor, heating melting is at liquid；140g is added
Formalin (37%) increases temperature to 50 DEG C, is stirred to react 90min；It adds 2.7g sodium hydroxide, increases temperature to 65 DEG C,
Continue to be stirred to react 30min；It is eventually adding remaining 30g formalin (37%), increases temperature to 80 DEG C, it is anti-that constant temperature continues stirring
Answer 30min.Cooling discharge obtains pure phenolic resin initial material rapidly after sampling viscosimetric is qualified.
B. 10g urea and 35g water is added in the pure phenolic resin initial material for taking 100g step A to obtain, and constant temperature stirs at 15 DEG C
20min obtains aqueous rock wool glue phenolic resin.
Comparative example 1
100g phenol, 130g formalin (37%), 6g sodium hydroxide are added in the reactor, 18g Urea is melt into liquid
State；Temperature is increased to 60 DEG C, is stirred to react 60min；After continue increase temperature to 75 DEG C, continue to be stirred to react 60min；Most
70g water is added afterwards, increases temperature to 95 DEG C, constant temperature continues to be stirred to react 30min.Rapid cooling discharge after sampling viscosimetric is qualified
Obtain resol resins.
Embodiment and the performance parameter of comparative example are shown in Table 1.
Comparative example analysis:
One, comparative example 1 is that feeding mode is one pot of all things while being added, therefore effect is not so good as the embodiment of the present invention；
(primary resin is claret to the color of the addition of modifying agent and urea effectively change resin, becomes orange-yellow after urea is added
Or faint yellow), increase aesthetics in the high temperature cure process of asbestos product.
There are two types of modes for existing urea adding method:
(1) urea, phenol, formaldehyde etc. one is added in pot simultaneously to react,
(2) urea is being added after formaldehyde-phenol reaction a period of time is first added.
The above addition manner is that urea will participate in polymerization reaction, needs to heat energy consumption or the extent of reaction more difficult to control,
More uncontrollable factors；
The present invention is cold, and technique of spelling is exactly polymerization reaction when urea does not need to participate in heating, but equally can be after cold spellings addition
Change color of resin after solidification.
Urea of the present invention does not participate in reacting in synthesis phase, so the polymer of urea-formaldehyde phenol three is not generated,
It is still urea itself, traditional handicraft can only have the free urea in part for having neither part nor lot in reaction.
The two comparison: urea can react under the high temperature conditions with formaldehyde, phenol, therefore urea is being consolidated under the technique
Free formaldehyde, phenol reactant during change and in resin.
One performance indicator of resol resins is free formaldehyde, free phenol content, the energy under present invention process
Reduce the index.
Two, step A reaction of the present invention is using three temperature rise periods: 60 DEG C of .50-；.65—70℃；.80—90℃.
Three, about catalyst
Sodium hydroxide: strong basicity, excellent catalytic effect, resin good water solubility, solid is high, but color of resin is deep；
Barium hydroxide: neutral and alkali, but easily precipitate, sodium hydroxide is compared, color of resin is shallow, beautiful；
Ammonium hydroxide: alkalescent, solid is lower, controls the bad water-soluble bad situation of easy appearance, and color of resin is more shallow；
Ammonium chloride: mainly saturate problem after the addition of change sodium hydroxide is only added a bit.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of aqueous rock wool glue phenolic resin, it is characterised in that the following steps are included:
A, under conditions of catalyst condensation reaction occurs for phenol and formalin, obtains pure phenolic resin initial material, formalin
It is added in two portions with catalyst,
Add phenol and catalyst in the reactor first, heating melting is at liquid；The formalin of volume is added for the first time, increases
Temperature is stirred to react 90-180min to 50-60 DEG C；Secondary addition catalyst increases temperature to 65-70 DEG C, continues to be stirred to react
30-120min；It is eventually adding remaining formalin, increases temperature to 80-90 DEG C, constant temperature continues to be stirred to react 30-60min；
B, modifying agent and diluent are added into the pure phenolic resin initial material that step A is obtained, obtains aqueous rock wool glue with phenolic aldehyde tree
Rouge.
2. preparation method according to claim 1, it is characterised in that: the quality of phenol and formalin in the step A
Than for 1:1.7-2.6.
3. preparation method according to claim 1 or 2, it is characterised in that: catalyst and phenol and formaldehyde in the step A
The mass ratio of pure material total amount is 0.03-0.05:1.
4. preparation method according to claim 3, it is characterised in that: the first time of formalin is added in the step A
Amount is 80%, and the concentration of formalin is 37%.
5. the preparation method according to claim 4, it is characterised in that: the first time additional amount of catalyst in the step A
For 66-68.6%.
6. preparation method according to claim 5, it is characterised in that: catalyst is sodium hydroxide, hydrogen-oxygen in the step A
Change one or both of barium, ammonium hydroxide, ammonium chloride.
7. preparation method according to claim 6, it is characterised in that: the addition of modifying agent and diluent in the step B
Mode is that constant temperature stirs at 10-20 DEG C, mixing time 20-30min.
8. preparation method according to claim 7, it is characterised in that: in the step B at the beginning of modifying agent and pure phenolic resin
The mass ratio of material is 0.1-0.2:1.
9. preparation method according to claim 8, it is characterised in that: modifying agent is urea in the step B.
10. preparation method according to claim 9, it is characterised in that: diluent is water in the step B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910371885.9A CN110092878A (en) | 2019-05-06 | 2019-05-06 | The preparation method of aqueous rock wool glue phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910371885.9A CN110092878A (en) | 2019-05-06 | 2019-05-06 | The preparation method of aqueous rock wool glue phenolic resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110092878A true CN110092878A (en) | 2019-08-06 |
Family
ID=67447036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910371885.9A Pending CN110092878A (en) | 2019-05-06 | 2019-05-06 | The preparation method of aqueous rock wool glue phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110092878A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112412293A (en) * | 2020-11-19 | 2021-02-26 | 江西朝阳机械有限公司 | Fireproof door leaf cotton arranging process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6646094B1 (en) * | 1999-06-17 | 2003-11-11 | Certainteed Corporation | Low emission formaldehyde resin and binder for mineral fiber insulation |
| CN102417570A (en) * | 2011-11-17 | 2012-04-18 | 江苏省新型复合研磨材料及制品工程技术研究中心 | Preparation method of environmentally-friendly phenolic resin |
| CN103555235A (en) * | 2013-11-03 | 2014-02-05 | 河北金舵建材科技开发有限公司 | Preparation method of high-performance resin adhesive for rock wool sizing |
| CN104403615A (en) * | 2014-11-12 | 2015-03-11 | 中南林业科技大学 | Modified phenolic resin adhesive and preparation method thereof |
| CN105601859A (en) * | 2016-01-19 | 2016-05-25 | 宜兴市宇球保温材料有限公司 | Water-soluble phenol-formaldehyde resin glue for rock wool and preparation method thereof |
| CN109180887A (en) * | 2018-08-10 | 2019-01-11 | 北京新时代寰宇科技发展有限公司 | Water-soluble rock wool Mo-phenolic resin and its adhesive, preparation method and application |
-
2019
- 2019-05-06 CN CN201910371885.9A patent/CN110092878A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6646094B1 (en) * | 1999-06-17 | 2003-11-11 | Certainteed Corporation | Low emission formaldehyde resin and binder for mineral fiber insulation |
| CN102417570A (en) * | 2011-11-17 | 2012-04-18 | 江苏省新型复合研磨材料及制品工程技术研究中心 | Preparation method of environmentally-friendly phenolic resin |
| CN103555235A (en) * | 2013-11-03 | 2014-02-05 | 河北金舵建材科技开发有限公司 | Preparation method of high-performance resin adhesive for rock wool sizing |
| CN104403615A (en) * | 2014-11-12 | 2015-03-11 | 中南林业科技大学 | Modified phenolic resin adhesive and preparation method thereof |
| CN105601859A (en) * | 2016-01-19 | 2016-05-25 | 宜兴市宇球保温材料有限公司 | Water-soluble phenol-formaldehyde resin glue for rock wool and preparation method thereof |
| CN109180887A (en) * | 2018-08-10 | 2019-01-11 | 北京新时代寰宇科技发展有限公司 | Water-soluble rock wool Mo-phenolic resin and its adhesive, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 刘瑞雪等: "《高分子材料》", 30 April 2018, 河南大学出版社 * |
| 张伟: "《多元共聚树脂胶黏剂化学与工艺学》", 31 October 2018, 文化发展出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112412293A (en) * | 2020-11-19 | 2021-02-26 | 江西朝阳机械有限公司 | Fireproof door leaf cotton arranging process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104693679B (en) | A kind of preparation method of nano silicon rosin modified phenolic resin | |
| CN103396650B (en) | A kind of modified alkyd resin based friction material | |
| CN103012703B (en) | Mid-temperature cured phenolic resin and preparation method thereof | |
| CN103588935B (en) | Take acrylic acid wastewater as the method that modified lignosulfonate water reducing agent prepared by raw material | |
| CN107082859A (en) | A kind of preparation method of the heat resistance modified phenolic resin of toughness reinforcing | |
| CN103709111A (en) | Synthetic method of etherified amino resin | |
| CN106750062A (en) | A kind of phenolic resin of modified by cardanol and the preparation method of phenolaldehyde moulding compound | |
| CN104262578A (en) | Method of synthesizing polyurethane curing agent by multi-batch charging manner and product thereof | |
| CN107201203A (en) | A kind of preparation method of boric acid modified thermostable phenolic resin adhesive | |
| CN104151515B (en) | Graphene modified furan resin and preparation method thereof | |
| CN110092878A (en) | The preparation method of aqueous rock wool glue phenolic resin | |
| CN103102462A (en) | Cashew nut shell oil modified phenolic resin as well as preparation method and application thereof | |
| CN108822778B (en) | Low-temperature fast curing environment-friendly adhesive and preparation method thereof | |
| CN103113840A (en) | Method for producing wood adhesive by using papermaking black liquor | |
| CN100432117C (en) | Method for bamboo liquifying substance phenolic glue | |
| CN104974320B (en) | Oxidation Cardanol Modified PF Resin and its preparation method and application | |
| CN109180887B (en) | Preparation method of molybdenum phenolic resin for water-soluble rock wool, adhesive and application thereof | |
| CN103613729B (en) | A kind of preparation method of modified phenolic resins | |
| CN103602298B (en) | Preparation method of phenolic resin adhesive | |
| CN101274976B (en) | Preparation for multicomponent copolycondensation phenolic resin | |
| CN105062390A (en) | Preparation method of adhesive for metal material packaging | |
| CN109535359A (en) | A method of alkali resistance phenolic resin is synthesized based on control solution ph | |
| CN105585993A (en) | Method for preparing isobutyl aldehyde modified urea-formaldehyde resin adhesive | |
| CN105153383B (en) | A kind of preparation method of high-quality phenolic resin | |
| CN102850499B (en) | Modified urea formaldehyde resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190806 |
|
| RJ01 | Rejection of invention patent application after publication |