CN1300228C - Sealed cell toughening foamed material and preparation thereof - Google Patents
Sealed cell toughening foamed material and preparation thereof Download PDFInfo
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- CN1300228C CN1300228C CNB2003101139653A CN200310113965A CN1300228C CN 1300228 C CN1300228 C CN 1300228C CN B2003101139653 A CNB2003101139653 A CN B2003101139653A CN 200310113965 A CN200310113965 A CN 200310113965A CN 1300228 C CN1300228 C CN 1300228C
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Abstract
The present invention relates to a sealed pore toughening foamed phenolic plastic and a preparation thereof. In the present invention, the molar ratio of phenol to formaldehyde for synthesizing modified phenolic resin is 1:1.30 to 2.50; modification auxiliary agents comprise a silicon intermediate, an ester compound and an ammonia compound; the foamed phenolic plastic is prepared from the following components: phenol, formaldehyde, a catalyst, a silicon intermediate, an ammonia compound and an ester compound; a foaming formula comprises resin, a surfactant, a foaming agent, a solidifying auxiliary agent and a solidifying agent. In preparation, all components are mixed and react, the ammonia compound and the ester compound are added, and modified resin is obtained by dewatering; the resin, etc. are mixed, the solidifying agent is added, all components are heated and solidified, and the foamed phenolic plastic is obtained. A specific chemical toughening method and the wonderful solidifying auxiliary agent are used, and three kinds of modification auxiliary agents are respectively added; paraffin hydrocarbon is used as a foaming agent without greenhouse effect coefficient, and the sealed pore toughening foamed phenolic plastic in a specific structure is obtained; the problems of obstructing the development of phenolic foam is solved; finally, the rate of sealed pores of phenolic foam is smaller than 85%, the brittleness is smaller than 25%, and the heat conduction coefficient is smaller than 0.025 W/m. k, and the condition is favorable for the popularization and the application of the foamed phenolic plastic.
Description
Technical field
The present invention relates to a kind of phenolic foamed plastics, especially closed pore toughening metlbond foam plastics and preparation method thereof.
Background technology
The present invention be directed to the porous plastics of R type resol and made thereof.The phenol formaldehyde foam that resol is produced, have thermal conductivity low, do not fire, the characteristic of low smoke and non-toxic, low value.The existing history for many years of phenol formaldehyde foam is that fire line is best in the insulating foam.Although these advantages are arranged, phenol formaldehyde foam is widespread use in insulation market not.Major cause is that phenol formaldehyde foam has more unfavorable thermal conductivity and can increase with the application time.Fragility also is a serious problem of phenolic foamed plastics in addition.
CN 1281480A patent proposes with (C
aF
b)
3N makes whipping agent, and manufacturing has fabulous heat-insulating property, improves brittle phenol formaldehyde foam.US 6,013, and No. 689 patent is used toughener or/and nucleator is produced the method for closed pore phenol formaldehyde foam.US 6,133, and No. 332 patent fluorochemicals are the phenol formaldehyde foam that whipping agent is made the steady heat conduction coefficient.US 6,472, No. 444 patent C
aF
bOC
2H
5Or trans 1,2-dichloroethene is made the phenol formaldehyde foam of steady heat conduction coefficient.
Summary of the invention
Although the technology of relevant phenol formaldehyde foam modification is many, a lot of technology have all been sacrificed the fire resistance of phenol formaldehyde foam in toughness reinforcing.The present invention proposes a kind of special chemical method for toughening that adopts just at this difficult problem, and preferred marvellous auxiliary curing agent is special to obtain a kind of structure, not only toughness reinforcing but also non-combustible closed pore toughening metlbond foam plastics.
The phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: (1.30～2.50), catalyzer are the binary complex body, and modified additive is silicon intermediate, ester compound, ammoniac compounds.Its component and content by weight are (is 100 parts with phenol):
Formaldehyde 100～220, catalyzer 0.8～8, silicon intermediate 2～10, ammoniac compounds 2～10, ester compound 2～10; Foaming formulation is a resin 100, tensio-active agent 1～5, whipping agent 2～12, solidifying agent 4～15.
Said catalyzer is selected from the binary complex body, can be at least a in highly basic and the metal oxide, and wherein highly basic is 0.5～5, and metal oxide is 0.3～3.
Tensio-active agent is selected from DC-190, DC-193, L-530, L-5310, L-158, tween 80, polysorbate40 or polysorbate60 etc.
Whipping agent is selected from Skellysolve A, iso-pentane, sherwood oil or alkane etc.
Solidifying agent can adopt organic acid, is selected from phenol sulfonic acid, tosic acid, xylene monosulfonic acid, oxalic acid or acetate etc.
The said closed pore toughening metlbond foam of the present invention plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 50～85 ℃ of reaction 40～60min, at 90～100 ℃ of reaction 100～150min;
2, add ammoniac compounds and continue reaction, temperature is 90-102 ℃, and the reaction times is 5-15min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent are mixed, add solidifying agent and heat 50～100 ℃, 10～120min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
The present invention has adopted special chemical method for toughening, add three class modified additives respectively, adopt alkane to make whipping agent, no global greenhouse effect coefficient obtains the special closed pore toughening metlbond foam plastics of structure, has solved the problem that hinders the phenol formaldehyde foam development, final phenol formaldehyde foam rate of closed hole is greater than 85%, fragility is less than 25%, and thermal conductivity helps applying of phenolic foamed plastics less than 0.025W/mk.
Embodiment
Following examples will the present invention is further illustrated.
Embodiment 1: the phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: 2, its component and content by weight are (is 100 parts with phenol): formaldehyde 170, catalyzer adopts highly basic 1, metal oxide 1, silicon intermediate 6, ammoniac compounds 5, ester compound 3; Foaming formulation is a resin 100, and tensio-active agent is selected L-1583.5 for use, and whipping agent is selected from alkane 8, and solidifying agent is selected from tosic acid 10.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 60 ℃ of reaction 50min, at 95 ℃ of reaction 150min;
2, add ammoniac compounds and continue reaction, temperature is 95 ℃, and the reaction times is 10min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent are mixed, add solidifying agent and stir 100s, heat 75 ℃, 80min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 2: the phenol and the formaldehyde mole ratio of its synthesis modification resol of closed pore toughening metlbond foam plastics are 1: 1.5, its component and content by weight are (is 100 parts with phenol): formaldehyde 125, catalyzer adopts highly basic 3, metal oxide 0.5, silicon intermediate 8, ammoniac compounds 2, ester compound 6; Foaming formulation is a resin 100, and tensio-active agent is selected for use
2, whipping agent is selected from sherwood oil 4, and solidifying agent is selected from phenol sulfonic acid 15.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 80 ℃ of reaction 45min, at 90 ℃ of reaction 120min;
2, add ammoniac compounds and continue reaction, temperature is 100 ℃, and the reaction times is 5min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent are mixed, add solidifying agent and stir 150s, heat 60 ℃, 50min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 3: the phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: 1.3, its component and content by weight are (is 100 parts with phenol): formaldehyde 110, catalyzer adopts highly basic 0.5, metal oxide 3, silicon intermediate 4, ammoniac compounds 10, ester compound 2; Foaming formulation is a resin 100, and tensio-active agent is selected " tween 80 " 4 for use, and whipping agent is selected from alkane 12, and solidifying agent is selected from tosic acid 8.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 60 ℃ of reaction 60min, at 100 ℃ of reaction 130min;
2, add ammoniac compounds and continue reaction, temperature is 100 ℃, and the reaction times is 5min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent are mixed, add solidifying agent and stir 80s, heat 80 ℃, 100min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 4: the phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: 1.8, its component and content by weight are (is 100 parts with phenol): formaldehyde 158, catalyzer adopts highly basic 5, metal oxide 0.3, silicon intermediate 10, ammoniac compounds 6, ester compound 10; Foaming formulation is a resin 100, and tensio-active agent is selected " DC-193 " 1 for use, and whipping agent is selected from alkane 10, and solidifying agent is selected from tosic acid 4.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 85 ℃ of reaction 50min, at 90 ℃ of reaction 100min;
2, add ammoniac compounds and continue reaction, temperature is 95 ℃, and the reaction times is 10min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent are mixed, add solidifying agent and stir 120s, heat 100 ℃, 120min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 5: the phenol and the formaldehyde mole ratio of its synthesis modification resol of closed pore toughening metlbond foam plastics are 1: 2.3, its component and content by weight are (is 100 parts with phenol): formaldehyde 200, catalyzer adopts highly basic 4, metal oxide 2, silicon intermediate 2, ammoniac compounds 8, ester compound 8; Foaming formulation is a resin 100, and tensio-active agent is selected " L-158 " 5 for use, and whipping agent is selected from alkane 2, and solidifying agent is selected from tosic acid 12.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 80 ℃ of reaction 40min, at 95 ℃ of reaction 110min;
2, add ammoniac compounds and continue reaction, temperature is 95 ℃, and the reaction times is 10min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent are mixed, add solidifying agent and stir 30s, heat 50 ℃, 30min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Embodiment 6: the phenol and the formaldehyde mole ratio of its synthesis modification resol of the said closed pore toughening metlbond foam of the present invention plastics are 1: 2.5, its component and content by weight are (is 100 parts with phenol): formaldehyde 220, catalyzer adopts highly basic 3.5, metal oxide 1.5, silicon intermediate 5, ammoniac compounds 4, ester compound 5; Foaming formulation is a resin 100, and tensio-active agent is selected " polysorbate60 " 3 for use, and whipping agent is selected from alkane 6, and solidifying agent is selected from tosic acid 6.
Closed pore toughening metlbond foam plastics preparation method's step is as follows:
1, presses its content with phenol, formaldehyde, silicon intermediate, catalyst mix, at 80 ℃ of reaction 55min, at 95 ℃ of reaction 125min;
2, add ammoniac compounds and continue reaction, temperature is 95 ℃, and the reaction times is 30min;
3, add ester compound, decompression dehydration down obtains modified resin;
4, resin, whipping agent, tensio-active agent are mixed, add solidifying agent and stir 50s, heat 90 ℃, 10min promptly gets the said closed pore toughening metlbond foam of the present invention plastics after the curing.
Claims (4)
1, closed pore toughening metlbond foam plastics is characterized in that the phenol of its synthesis modification resol and formaldehyde mole ratio are 1: 1.30～2.50, and catalyzer is highly basic and metal oxide, and modified additive is silicon intermediate, ester compound and ammoniac compounds; Its component and content by weight are: phenol 100, formaldehyde 100～220, catalyzer 0.8～8, silicon intermediate 2～10, ammoniac compounds 2～10, ester compound 2～10, wherein, catalyzer for 0.8～8, highly basic are 0.5～5, and metal oxide is 0.3～3; Foaming formulation is a resin 100, tensio-active agent 1～5, and whipping agent 2～12, solidifying agent 4～15, described solidifying agent is selected from phenol sulfonic acid, tosic acid or xylene monosulfonic acid.
2, closed pore toughening metlbond foam plastics as claimed in claim 1 is characterized in that said tensio-active agent is selected from DC-190, DC-193, L-530, L-5310, L-158, tween 80, polysorbate40 or polysorbate60.
3, closed pore toughening metlbond foam plastics as claimed in claim 1 is characterized in that said whipping agent is selected from Skellysolve A, iso-pentane or sherwood oil.
4, closed pore toughening metlbond foam plastics preparation method as claimed in claim 1 is characterized in that its step is as follows:
1), presses its component and content with phenol, formaldehyde, silicon intermediate and catalyst mix, at 55～85 ℃ of reaction 40～60min, at 90～100 ℃ of reaction 100～150min, described catalyzer is selected from highly basic and metal oxide, wherein highly basic is 0.5～5, and metal oxide is 0.3～3;
2), add ammoniac compounds and continue reaction, temperature is 85～100 ℃, the reaction times is 5～30min;
3), add ester compound, decompression is dehydration down, obtains modified resin;
4), resin, whipping agent and tensio-active agent are mixed, add solidifying agent and heat 50～100 ℃, 10～120min, after the curing promptly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101139653A CN1300228C (en) | 2003-11-05 | 2003-11-05 | Sealed cell toughening foamed material and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101139653A CN1300228C (en) | 2003-11-05 | 2003-11-05 | Sealed cell toughening foamed material and preparation thereof |
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| Publication Number | Publication Date |
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| CN1613897A CN1613897A (en) | 2005-05-11 |
| CN1300228C true CN1300228C (en) | 2007-02-14 |
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| CNB2003101139653A Expired - Fee Related CN1300228C (en) | 2003-11-05 | 2003-11-05 | Sealed cell toughening foamed material and preparation thereof |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033307B (en) * | 2006-03-10 | 2011-06-08 | 上海尖端工程材料有限公司 | Method of preparing pnenolic aldehyde foam from modified foamable phenolic resin |
| CN101962971B (en) * | 2009-07-24 | 2012-09-19 | 苏州美克思科技发展有限公司 | Phenolic foam insulation board for high-strength walls and manufacturing method thereof |
| CN103073740A (en) * | 2013-01-29 | 2013-05-01 | 山东圣泉化工股份有限公司 | Preparation method of phenolic foamed plastic |
| CN103254565B (en) * | 2013-06-04 | 2016-01-27 | 上海海事大学 | A kind of preparation method of toughening modifying phenol formaldehyde foam |
| CN105111674A (en) * | 2015-08-31 | 2015-12-02 | 沈阳化工大学 | Ionic liquid improved low-acidity and high-activity phenolic resin curing agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065077A (en) * | 1992-04-10 | 1992-10-07 | 沈阳化工学院 | Modified phenolic foam |
| CN1030836C (en) * | 1991-12-07 | 1996-01-31 | 中国科学院广州化学所 | Method for prodcuing absorbent phenolic foam plastics |
| CN1073129C (en) * | 1994-06-09 | 2001-10-17 | 欧文斯科尔宁格公司 | Non-CFC foam produced using perfluoroalkanes |
-
2003
- 2003-11-05 CN CNB2003101139653A patent/CN1300228C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030836C (en) * | 1991-12-07 | 1996-01-31 | 中国科学院广州化学所 | Method for prodcuing absorbent phenolic foam plastics |
| CN1065077A (en) * | 1992-04-10 | 1992-10-07 | 沈阳化工学院 | Modified phenolic foam |
| CN1073129C (en) * | 1994-06-09 | 2001-10-17 | 欧文斯科尔宁格公司 | Non-CFC foam produced using perfluoroalkanes |
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Owner name: XIAMEN GOOT ADVANCED MATERIAL CO.,LTD. Free format text: FORMER NAME OR ADDRESS: XINFENGJI INDUSTRY CO LTD, XIAMEN |
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Address after: 361021 No. 99, Liantang Road, North District, Fujian, Xiamen, Jimei Patentee after: Gaotegao New Material Co., Ltd., Xiamen Address before: 361021 No. 99, Liantang Road, North District, Fujian, Xiamen, Jimei Patentee before: Xinfengji Industry Co Ltd, Xiamen |
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Granted publication date: 20070214 Termination date: 20101105 |