CN103881632A - Composite curing agent and preparation method thereof - Google Patents
Composite curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN103881632A CN103881632A CN201410106179.9A CN201410106179A CN103881632A CN 103881632 A CN103881632 A CN 103881632A CN 201410106179 A CN201410106179 A CN 201410106179A CN 103881632 A CN103881632 A CN 103881632A
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- CN
- China
- Prior art keywords
- resorcinol
- curing agent
- composite curing
- copolymer resins
- parts
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- 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.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 23
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002472 Starch Polymers 0.000 claims abstract description 17
- 235000019698 starch Nutrition 0.000 claims abstract description 17
- 239000008107 starch Substances 0.000 claims abstract description 17
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 11
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 11
- 108010073771 Soybean Proteins Proteins 0.000 claims abstract description 9
- 235000019710 soybean protein Nutrition 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 14
- 229920002866 paraformaldehyde Polymers 0.000 claims description 14
- 238000004898 kneading Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims description 7
- 239000011147 inorganic material Substances 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- -1 chalk Chemical compound 0.000 claims 1
- 239000002023 wood Substances 0.000 abstract description 17
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 229920001568 phenolic resin Polymers 0.000 abstract description 3
- QDNBHWFDWXWFTG-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1.OC1=CC=CC(O)=C1 QDNBHWFDWXWFTG-UHFFFAOYSA-N 0.000 abstract 2
- 239000000805 composite resin Substances 0.000 abstract 1
- 230000001788 irregular Effects 0.000 abstract 1
- 229920006324 polyoxymethylene Polymers 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 239000003292 glue Substances 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000011615 Pinus koraiensis Nutrition 0.000 description 1
- 240000007263 Pinus koraiensis Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a resorcinol-formaldehyde resin/resorcinol-phenol-formaldehyde resin composite curing agent and a preparation method thereof. The composite curing agent is characterized by comprising the following components in parts by weight: 5-20 parts of polyformaldehyde or hexamethylenetetramine, 5-20 parts of starch or soybean protein isolate and 5-20 parts of inorganic substance powder. The composite curing agent has the advantages of normative technique and the like, and is simple to operate and easy to implement. The active period of the composite curing agent is more than 4 hours when being compounded with the resorcinol-formaldehyde resin and resorcinol-phenol-formaldehyde copolymer resin; and the composite curing agent can satisfy the requirements for active period of HLULAM, wood glulam beams, wood glulam columns, I beams and other wood structure components as well as large-size wood glulam furniture and other products with various shapes and sizes (especially irregular shapes and large size), and enables the bonded structure to have excellent physical and mechanical properties and weather resistance.
Description
Technical field
What the present invention relates to is composite curing agent of a kind of resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins and preparation method thereof, belongs to wood adhesive and manufactures field.
Background technology
Structural Laminated Wood splicing is thermoplastic resin with resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins, and the proportioning raw materials of resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins should meet following condition:
Formaldehyde in resorcinol-formaldehyde copolymer resins (F) should be less than 1(F/R < 1 with the mol ratio of Resorcinol (R)); In Resorcinol-P-F copolymer resins formaldehyde (F) and Resorcinol (R) and phenol (P) and mol ratio should be less than 1(F/(R+P) < 1).Often take paraformaldehyde or hexamethylenetetramine as solidifying agent, to realize normal temperature fast setting.Due to the structural feature of Resorcinol, the reactive behavior of itself and formaldehyde is high, take paraformaldehyde or hexamethylenetetramine in conjunction with flour during as solidifying agent, curing reaction speed is exceedingly fast, after causing impregnation, the active phase is generally in 30 minutes, cannot meet different shape size, especially irregularly shaped and large size GLULAM, glued wood beam, glued wood post, the requirement of the product such as tool processing to the active phase of the whole family of the wood structures such as I-beam and Large Real wood glue, in the patent of application number 201310164550.2, mention a kind of Resorcinol modified phenolic resins composite curing agent and preparation method thereof, mainly solving existing solidifying agent exists glue performance poor, when use, produce the harmful problem of dust, about solidifying agent, this important construction factor that affects of active phase of Resorcinol modified phenolic resins was not mentioned.
Summary of the invention
What the present invention proposed is composite curing agent of a kind of resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins and preparation method thereof, its object is intended to solve when existing solidifying agent adds resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins and causes resin too short working life, cannot meet above two resinoids glued joint needs problem for large-size wood structure member.
Technical solution of the present invention: resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins composite curing agent, is characterized in that composite curing agent is made up of paraformaldehyde or hexamethylenetetramine, starch or soybean protein isolate and inorganic material powders; Its weight part ratio is 5-20:5-20:5-20.
The preparation method of resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins composite curing agent, comprises the steps:
1) by paraformaldehyde or hexamethylenetetramine powder, starch soybean protein isolate and inorganic material powders by weight 5-20:5-20:5-20 mediate evenly;
2) in kneading process, add water, make mixture water ratio at 14-20%;
3) by water ratio the kneading mixture between 14-20% to be placed in bulking machine expanded, the temperature 100-160 ℃ of bulking machine, bulking pressure is at 5.0-8.5MPa, the gelatinization rate of starch or the slaking rate of soybean protein isolate are at 70-90%; Be the above powder of 100 order by again pulverizing after puff or the cryodrying of slaking thing; Complete the preparation of composite curing agent.
Beneficial effect of the present invention:
1) in composite curing agent component, paraformaldehyde (or hexamethylenetetramine) reacts so that resin solidification with the methylol in resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins; The slow-released carrier that becomes paraformaldehyde (or hexamethylenetetramine) after starch (or soybean protein isolate) is crosslinked with paraformaldehyde (or hexamethylenetetramine) after expanded gelatinization (or slaking), to extend the active phase of resin, and increases the snappiness of glue-line; Inorganic material powders is for reducing using glue cost, and opposing glue-line shrinks the internal stress producing, and improves structural strength and the ageing-resistant performance of glue-line.
2) as composite curing agent, coordinate with resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins, the active phase of resin is reached more than 4 hours, can meet different shape size, the requirement of product processing to the active phase such as tool of the whole family of the wood structures such as especially irregularly shaped and large size GLULAM, glued wood beam, glued wood post, I-beam and Large Real wood glue, and make bonded structure there is excellent physical and mechanical property and weather resistance.
Embodiment
The each embodiment of described composite curing agent is raw materials used and with scale, as table 1.
Table 1
Embodiment 1
By 5 parts, paraformaldehyde powder, 10 parts of starch and 5 parts of kneadings of china clay evenly, add water 5 parts in kneading process, making mixture water ratio is 20%; Water ratio 20% is mediated to uniform mixture, and to be placed in bulking machine expanded, and the temperature of bulking machine is at 120 ℃, and bulking pressure is at 5.0MPa, the gelatinization rate 70% of starch; Be the above powder of 200 order by again pulverizing after puff cryodrying; Complete the preparation of composite curing agent.
Embodiment 2
By 10 parts, paraformaldehyde powder, 10 parts of starch and 10 parts of kneadings of chalk evenly, add water 7.5 parts in kneading process, making mixture water ratio is 20%; Water ratio 20% is mediated to uniform mixture, and to be placed in bulking machine expanded, and the temperature of bulking machine is at 130 ℃, and bulking pressure is at 5.5MPa, the gelatinization rate 72% of starch; Be the above powder of 200 order by again pulverizing after puff cryodrying; Complete the preparation of composite curing agent.
Embodiment 3
By 15 parts, paraformaldehyde powder, 10 parts of starch and 5 parts of kneadings of kaolin evenly, add water 7.5 parts in kneading process, making mixture water ratio is 20%; Water ratio 20% is mediated to uniform mixture, and to be placed in bulking machine expanded, and the temperature of bulking machine is at 140 ℃, and bulking pressure is at 6.0MPa, the gelatinization rate 75% of starch; Be the above powder of 200 order by again pulverizing after puff cryodrying; Complete the preparation of composite curing agent.
Embodiment 4
By 20 parts, paraformaldehyde powder, 5 parts of starch and 5 parts of kneadings of kaolin evenly, add water 7.5 parts in kneading process, making mixture water ratio is 20%; Water ratio 20% is mediated to uniform mixture, and to be placed in bulking machine expanded, and the temperature of bulking machine is at 100 ℃, and bulking pressure is at 6.5MPa, the gelatinization rate 80% of starch; Be the above powder of 200 order by again pulverizing after puff cryodrying; Complete the preparation of composite curing agent.
Embodiment 5,9,13, preparation method is identical with embodiment 1 except raw material consumption.
Embodiment 6,10,14, preparation method is identical with embodiment 2 except raw material consumption.
Embodiment 7,11,15, preparation method is identical with embodiment 3 except raw material consumption.
Embodiment 8,12,16, preparation method is identical with embodiment 4 except raw material consumption.
Test example 1, the solidifying agent using the present invention as Resorcinol-P-F copolymer resins tackiness agent is for the test of GLULAM Cold-press adhesion, and the proportioning of tackiness agent host and solidifying agent is in table 2.
Table 2
Using the present invention as Resorcinol-P-F copolymer resins solidifying agent, for GLULAM cold pressure test, wood raw material used is Korean pine, and raw materials size is that 100cm × 20cm × 2cm(is long × wide × thick), 10 plate rift grain assembly room temperature gummeds.
Gummed sample detects through national wood-based plate Quality Supervision and Inspection Center, and detected result is in table 3, and detected result all meets GB/T 26899-2011 standard.
Table 3
Claims (4)
1. the composite curing agent of resorcinol-formaldehyde copolymer resins and Resorcinol-P-F copolymer resins, is characterized in that composite curing agent is made up of paraformaldehyde or hexamethylenetetramine, starch or soybean protein isolate and inorganic material powders; Its weight part is 5-20:5-20:5-20.
2. resorcinol-formaldehyde copolymer resins as claimed in claim 1 and Resorcinol-P-F copolymer resins composite curing agent, is characterized in that described paraformaldehyde or hexamethylenetetramine, starch or soybean protein powder, inorganic material powders are all processed into the above powder of 100 order.
3. resorcinol-formaldehyde copolymer resins as claimed in claim 1 and Resorcinol-P-F copolymer resins composite curing agent, is characterized in that described inorganic material powders comprises china clay, chalk, kaolin or ore powder.
4. the preparation method of resorcinol-formaldehyde copolymer resins as claimed in claim 1 and Resorcinol-P-F copolymer resins composite curing agent, is characterized in that the method comprises the steps:
1) by paraformaldehyde or hexamethylenetetramine powder, starch soybean protein isolate and inorganic material powders by weight 5-20:5-20:5-20 mediate evenly;
2) in kneading process, add water, make mixture water ratio at 14-20%;
3) by water ratio the kneading mixture between 14-20% to be placed in bulking machine expanded, the temperature 100-160 ℃ of bulking machine, bulking pressure is at 5.0-8.5MPa, the gelatinization rate of starch or the slaking rate of soybean protein isolate are at 70-90%; Be the above powder of 100 order by again pulverizing after puff or the cryodrying of slaking thing; Complete the preparation of composite curing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410106179.9A CN103881632B (en) | 2014-03-21 | 2014-03-21 | Composite curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410106179.9A CN103881632B (en) | 2014-03-21 | 2014-03-21 | Composite curing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103881632A true CN103881632A (en) | 2014-06-25 |
| CN103881632B CN103881632B (en) | 2015-06-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410106179.9A Expired - Fee Related CN103881632B (en) | 2014-03-21 | 2014-03-21 | Composite curing agent and preparation method thereof |
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| Country | Link |
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| CN (1) | CN103881632B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440971A (en) * | 2015-11-30 | 2016-03-30 | 中南林业科技大学 | Curing agent of adhesive for laminated wood |
| CN106318294A (en) * | 2016-08-23 | 2017-01-11 | 北京林业大学 | Preparing method of pyrolytic tar resorcinol formaldehyde resin tackifier for use in timberwork building materials |
| CN107090255A (en) * | 2017-06-23 | 2017-08-25 | 江苏祥豪实业股份有限公司 | A kind of wood adhesive composite curing agent and preparation method thereof |
| CN111170663A (en) * | 2019-12-28 | 2020-05-19 | 肇庆市武大环境技术研究院 | Sea mud curing agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994028A (en) * | 2011-09-15 | 2013-03-27 | 吕元 | Phenolic resin adhesive for plywood |
| CN103214787A (en) * | 2013-05-07 | 2013-07-24 | 黑龙江省木材科学研究所 | Resorcinol modified phenolic resin composite curing agent and preparation method thereof |
-
2014
- 2014-03-21 CN CN201410106179.9A patent/CN103881632B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102994028A (en) * | 2011-09-15 | 2013-03-27 | 吕元 | Phenolic resin adhesive for plywood |
| CN103214787A (en) * | 2013-05-07 | 2013-07-24 | 黑龙江省木材科学研究所 | Resorcinol modified phenolic resin composite curing agent and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105440971A (en) * | 2015-11-30 | 2016-03-30 | 中南林业科技大学 | Curing agent of adhesive for laminated wood |
| CN106318294A (en) * | 2016-08-23 | 2017-01-11 | 北京林业大学 | Preparing method of pyrolytic tar resorcinol formaldehyde resin tackifier for use in timberwork building materials |
| CN106318294B (en) * | 2016-08-23 | 2019-03-26 | 北京林业大学 | The preparation method of timber structure building materials pyrolysis oil resorcinol formaldehyde resin adhesive |
| CN107090255A (en) * | 2017-06-23 | 2017-08-25 | 江苏祥豪实业股份有限公司 | A kind of wood adhesive composite curing agent and preparation method thereof |
| CN107090255B (en) * | 2017-06-23 | 2018-10-02 | 江苏祥豪实业股份有限公司 | A kind of wood adhesive composite curing agent and preparation method thereof |
| CN111170663A (en) * | 2019-12-28 | 2020-05-19 | 肇庆市武大环境技术研究院 | Sea mud curing agent |
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| Publication number | Publication date |
|---|---|
| CN103881632B (en) | 2015-06-17 |
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Application publication date: 20140625 Assignee: Nantong Er Xin Wood Industry Co.,Ltd. Assignor: Nanjing Forestry University Contract record no.: 2018320000197 Denomination of invention: Composite curing agent and preparation method thereof Granted publication date: 20150617 License type: Common License Record date: 20181011 |
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Application publication date: 20140625 Assignee: SHANDONG RUISAN CHEMICAL TECHNOLOGY CO.,LTD. Assignor: Nanjing Forestry University Contract record no.: 2018320000237 Denomination of invention: Composite curing agent and preparation method thereof Granted publication date: 20150617 License type: Common License Record date: 20181025 |
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