CN85109503A - The preparation method of phenol modified urea-formaldehyde resins and application - Google Patents
The preparation method of phenol modified urea-formaldehyde resins and application Download PDFInfo
- Publication number
- CN85109503A CN85109503A CN 85109503 CN85109503A CN85109503A CN 85109503 A CN85109503 A CN 85109503A CN 85109503 CN85109503 CN 85109503 CN 85109503 A CN85109503 A CN 85109503A CN 85109503 A CN85109503 A CN 85109503A
- Authority
- CN
- China
- Prior art keywords
- phenol
- urea
- formaldehyde
- modified urea
- formaldehyde resins
- 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
Landscapes
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
Phenol modified urea-formaldehyde resins preparation method and application.Phenol modified urea-formaldehyde resins of the present invention is that main raw material is synthetic by phenol, urea, formaldehyde.The mole ratio of phenol and urea is 1: 1～4.The mole ratio of formaldehyde and phenol and urea is 1.5～2.2: 1.Resin becomes oligopolymer by phenol with formaldehyde condensation under alkaline condition, add urea then, prepares water miscible phenol modified urea-formaldehyde resins.This resin has with short production cycle, free formaldehyde, low, water-fast, the good heat resistance of free phenol content, characteristics such as raw materials cost is low.Can be widely used in dry-process fiberboard, shaving board, shaving board, decorative sheet and veneer sheet manufacturing.
Description
The present invention relates to a kind of is the preparation method of the direct synthesizing water-solubility phenol modified urea-formaldehyde resins of main raw material and its application by phenol, urea, formaldehyde.
Wood-based panel industry mainly uses urea aldehyde, melamine modified urea-formaldehyde, melamino-formaldehyde, phenolic aldehyde and polyvinyl acetate etc.Urea aldehyde, melamine modified urea-formaldehyde, polyvinyl acetate water tolerance, thermotolerance are relatively poor.Urea aldehyde, cyanurotriamide modified urea resin also have the free formaldehyde content height, and life stage is short, be easy to generate the surface and shift to an earlier date shortcomings such as cured layer in fiberboard processing.Though phenolic aldehyde and terpolycyantoamino-formaldehyde resin have water tolerance and thermotolerance preferably, the content of free aldehyde of resin is also lower, and the raw materials cost of resin is higher.Also study both at home and abroad for this reason and use phenol modified urea-formaldehyde resins.
The domestic and international phenol modified urea-formaldehyde resins of report, the mole ratio of phenol and urea is respectively 1: 10～50(GB1254786, US3547868) with 1: 0.4～0.8(SU959889).Studies show that when the mole ratio of phenol and urea is 1: 10～50, though the free formaldehyde content of resin can reduce, the water tolerance of resin and thermotolerance and urea-formaldehyde resin are approaching.When the mole ratio of phenol and urea was 1: 0.4～0.8, the raw materials cost of resin had increased considerably again.
The preparation method of phenol modified urea-formaldehyde resins has two kinds both at home and abroad, a kind of is direct synthesis technique (GB1254786, US3547868), another kind is to mix the glue method, promptly prepare phenolic aldehyde and urea-formaldehyde resin at first respectively, be mixed in proportion use (JP5808476) then, complicated process of preparation, and only be used for veneer sheet and decorative sheet.
External phenol modified urea-formaldehyde resins prepares under acidic conditions, at first adds urea and formaldehyde during reaction, generate add again behind the oligopolymer phenol (GB1254786, US3547868).Production cycle is longer.
The objective of the invention is under alkaline condition, is the direct synthesizing water-solubility of main raw material by phenol, urea, formaldehyde, and water tolerance, thermotolerance be phenol modified urea-formaldehyde resins preferably.The surface of in use reducing dry-process fiberboard shifts to an earlier date cured layer, reduces the free formaldehyde content of artificial board.
Phenol-modified urea aldehyde preparation technology of the present invention is as follows:
1, phenol modified urea-formaldehyde resins is mainly by industrial formol, phenol, urea condensation.
2, one of feature of the present invention is that the mole ratio of phenol and urea is 1: 1～4.
3, the mole ratio of formaldehyde and phenol and urea is 1.5～2.2: 1.
4, two of feature of the present invention is to prepare phenol modified urea-formaldehyde resins under alkaline condition.PH conditioning agent commonly used is sodium hydroxide, hydrated barta, ammoniacal liquor, organic amine, organic alcohol amine etc.PH control 7.5～10 during reaction.
5, three of feature of the present invention is at first under alkaline condition, becomes oligopolymer by phenol with formaldehyde condensation, adds urea then, the preparation phenol modified urea-formaldehyde resins.
6, four of feature of the present invention is the phenol modified urea-formaldehyde resins that prepare low-free formaldehyde, free phenol content in the reaction times of 2～4h.
Preparation process is as follows:
Stoichiometric formaldehyde once adds in the reactor of being with stirring, chuck and reflux exchanger, stirs to add the stoichiometric phenol of fused down.PH is 7.5～10 with the control of PH conditioning agent.Feed steam then in the chuck, the heat-up rate of control material is 0.5～1.5 ℃/min.When the reaction mass temperature reached 40～80 ℃, reactor should stop heating.When temperature of reaction reaches 85 ℃, begin to calculate the reaction times more than 85 ℃, add stoichiometric urea behind controlling reaction time 10～40min, reacting 10～50min more than 85 ℃.Must constantly observe the cloud in the drop of resin entry in the reaction process, or,, cool to rapidly below 40 ℃ when resin reaches service requirements with being coated with-4 glasss of specific viscosities of measuring resin.Yield is greater than 99%.Production cycle 2～4h.
Resin quality is as follows:
Solid content: 48 ± 2%
Proportion (20 ℃): 1.17～1.20
Specific viscosity (being coated with-4,25 ℃): 13～30s(controls according to service requirements)
Curing speed (150 ℃): 40～120s(controls according to service requirements)
Free formaldehyde content:＜0.5%
Free phenol content:＜1.8%
Can be by bromide content: 6～14%
Life stage (25 ℃): 〉=1 month
PH：7.5～10
Characteristics such as it is simple that phenol modified urea-formaldehyde resins of the present invention has preparation technology, with short production cycle, and the resin free formaldehyde, free phenol content is low, heat-resisting, water resistance is good, and the resin staging life is long.Under same applying glue raw materials cost, the adhesive property of phenol modified urea-formaldehyde resins, water-fast, resistance toheat obviously are better than other resin (seeing Table 1, table 2).Phenol modified urea-formaldehyde resins is applied to dry medium density fibreboard, and not only the free formaldehyde content of plate can be lower than the 50mg/100g plate, and the surface of fiberboard shifts to an earlier date cured layer and is starkly lower than urea aldehyde or cyanurotriamide modified urea resin.Phenol modified urea-formaldehyde resins can be widely used in dry-process fiberboard, shaving board, shaving board, decorative sheet and veneer sheet.
The thermotolerance of table 1 different resins
Example one
Reactor is preheated to 40 ℃, adds fused phenol 240kg, the sodium hydroxide 13kg of concentration 30% stirs the formaldehyde 1014kg that adds content 36.5% down.Regulate PH to 8.Reacting kettle jacketing feeds steam makes material slowly be warming up to 90 ℃, 0.8 ℃/min of heat-up rate.React 20min more than 90 ℃, adding the urea 332kg of content 96%.When occurring preferably cloud in the drop of resin entry, cooling rapidly in 60 ℃, adds solidifying agent 8kg.At last resin is chilled to room temperature.Production cycle 3h, resin yield 99.7%.Resin property is as follows:
Solid content: 49.6%
PH：8.15
Viscosity (being coated with-4,25 ℃): 14.1s
Free formaldehyde content: be listed as American and French can't measuring.
Free phenol content: 0.41%
Curing speed (150 ℃): 67.5s
Can be by bromide content: 7.69%
Life stage (25 ℃): 2 months
Application example one
Bagasse is through defibrator process, freeness 18s.Apply cost (as shown in table 2) by suitable resin raw material, add phenol-modified urea aldehyde, urea aldehyde and the cyanurotriamide modified urea resin of phenolic aldehyde, different proportionings in proportion.Water-resisting agent (paraffin) applied amount is 1.5% of a bone dry fiber.After hot-forming, fibreboard performance is as shown in table 2.
Application example two
Bagasse is through defibrator process, freeness 18s.The phenol modified urea-formaldehyde resins applied amount is a bone dry fiber 8%.
The bagasse dry horminess fibreboard performance of table 2 different resins
The paraffin applied amount is 1.5% of a bone dry fiber.Hot-forming back fiberboard quality is as follows:
Unit weight: 0.75t/m
3
Thickness of slab: 10mm
Water ratio: 5%
MOR: 260kg/cm
2
Internal bond: 6.4kg/cm
2
Water-intake rate: 16%
Thickness swelling rate: 6%
Pressed-fibre board free formaldehyde content: 19mg/100g plate
Application example three
Behind the industry particle drying, apply phenol modified urea-formaldehyde resins 8%, the paraffin applied amount is 1.5% of an over dry flaking.Hot-forming back shaving board quality is as follows:
Unit weight: 0.74t/m
3
Thickness of slab: 18mm
MOR: 195kg/cm
2
Internal bond: 4.88kg/cm
2
Water-intake rate (2h): 5.77%
Thickness swelling rate (2h): 3.11%
Claims (4)
1, phenol modified urea-formaldehyde resins is mainly synthetic by raw materials such as phenol, urea, formaldehyde.The invention is characterized in (PH7.5～10) direct synthesizing phenol modified urea-formaldehyde resin under alkaline condition.
2, according to claim 1, the mole ratio that the invention is characterized in phenol and urea is 1: 1～4.
3, according to claim 1, the invention is characterized in and under alkaline condition, at first make oligopolymer, and then add urea, synthesizing phenol modified urea-formaldehyde resin by phenol and formaldehyde reaction.
4, as described in the claim 1,2 or 3, the invention is characterized in that phenol modified urea-formaldehyde resins can be widely used in dry-process fiberboard, shaving board, shaving board, decorative sheet and veneer sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85109503 CN85109503A (en) | 1985-11-22 | 1985-11-22 | The preparation method of phenol modified urea-formaldehyde resins and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85109503 CN85109503A (en) | 1985-11-22 | 1985-11-22 | The preparation method of phenol modified urea-formaldehyde resins and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85109503A true CN85109503A (en) | 1986-07-23 |
Family
ID=4796369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85109503 Pending CN85109503A (en) | 1985-11-22 | 1985-11-22 | The preparation method of phenol modified urea-formaldehyde resins and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85109503A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140156A (en) * | 2011-01-25 | 2011-08-03 | 中国林业科学研究院林产化学工业研究所 | Preparation method of phenol-urea-formaldehyde resin adhesive for E0-grade outdoor plywood |
| CN102850499A (en) * | 2012-03-21 | 2013-01-02 | 山东圣泉化工股份有限公司 | Modified urea formaldehyde resin and preparation method thereof |
| CN103571409A (en) * | 2012-07-31 | 2014-02-12 | 苏州维艾普新材料有限公司 | High-temperature resistant and fire-retardant adhesive and preparation method thereof |
| CN110387022A (en) * | 2019-07-30 | 2019-10-29 | 中原工学院 | A method of ureaformaldehyde fiber is prepared by modification by copolymerization |
-
1985
- 1985-11-22 CN CN 85109503 patent/CN85109503A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140156A (en) * | 2011-01-25 | 2011-08-03 | 中国林业科学研究院林产化学工业研究所 | Preparation method of phenol-urea-formaldehyde resin adhesive for E0-grade outdoor plywood |
| CN102140156B (en) * | 2011-01-25 | 2013-01-02 | 中国林业科学研究院林产化学工业研究所 | Preparation method of phenol-urea-formaldehyde resin adhesive for E0-grade outdoor plywood |
| CN102850499A (en) * | 2012-03-21 | 2013-01-02 | 山东圣泉化工股份有限公司 | Modified urea formaldehyde resin and preparation method thereof |
| CN102850499B (en) * | 2012-03-21 | 2014-09-03 | 山东圣泉化工股份有限公司 | Modified urea formaldehyde resin and preparation method thereof |
| CN103571409A (en) * | 2012-07-31 | 2014-02-12 | 苏州维艾普新材料有限公司 | High-temperature resistant and fire-retardant adhesive and preparation method thereof |
| CN110387022A (en) * | 2019-07-30 | 2019-10-29 | 中原工学院 | A method of ureaformaldehyde fiber is prepared by modification by copolymerization |
| CN110387022B (en) * | 2019-07-30 | 2022-02-15 | 中原工学院 | Method for preparing urea-formaldehyde fiber through copolymerization modification |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5173527A (en) | Fast cure and pre-cure resistant cross-linked phenol-formaldehyde adhesives and methods of making same | |
| CN1177009C (en) | Modified water resistant low temperature white emulsoid | |
| RU2491301C2 (en) | Thermoreactive polymers | |
| JPH0696244B2 (en) | How to make particles or fiberboard | |
| CN1252780A (en) | Method of treating a lignocelulosic material or an expanded mineral to form a finished product | |
| CN1099328A (en) | Light shaving board and its producing process | |
| CN1884332A (en) | Urea-formaldehyde resin and its preparation method | |
| CN108818808A (en) | A kind of preparation method of water-fast bamboo-wood plyboard | |
| CN85109503A (en) | The preparation method of phenol modified urea-formaldehyde resins and application | |
| US3839251A (en) | Phenolic resin and process for making same | |
| CN110003829B (en) | Preparation method of environment-friendly modified urea-formaldehyde resin adhesive | |
| CN1048719A (en) | The binder composition that is used for sheet and/or fibrous material | |
| RU2154652C2 (en) | Method of preparing urea-modified phenol resin binder intended for treating chip of middle layers of wood chip boards | |
| US3903041A (en) | Composition board and process | |
| CN1044881C (en) | Artificial straw board and its manufacturing technology | |
| SE464087B (en) | APPLICATION OF A CARBAMIDE-FORMAL HEADLINE IN THE PREPARATION OF AGGLOMERATED WOODEN PANELS AND CRYSTAL DISK | |
| CN103254860B (en) | UFIM adhesive and preparation method thereof and UFIM glued ecological plant fiber board and particle board | |
| CN85109469A (en) | Bagasse dry process fiberboard is made | |
| SU1118655A1 (en) | Composition for manufacturing fiber boards by dry method | |
| CN112028585A (en) | Heat-insulating gypsum board and production method thereof | |
| CN108948649A (en) | A kind of resin base composite friction plate | |
| JPS5925656B2 (en) | Manufacturing method of dry-formed plate | |
| CN116572336B (en) | Bamboo-wood board modifier and preparation method and application thereof | |
| CN1037348A (en) | The manufacturing of low-toxic composite urea-formaldehyde resin | |
| CN113461886B (en) | Fast-curing phenolic resin and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |