CN107325479A - Plasticizing phenol formaldehyde warming plate and preparation method thereof - Google Patents
Plasticizing phenol formaldehyde warming plate and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/32—Modified amine-aldehyde condensates
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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Abstract
The present invention proposes a kind of plasticizing phenol formaldehyde warming plate and preparation method thereof, including following raw material：4~8 parts of 50~70 parts of phenol-formaldehyde resin modified, 15~25 parts of glass bead, 1~3 part of phenolic resin fluidity improver, 4~8 parts of toughener, 4~8 parts of polyethylene glycol, 3~6 parts of silicone acrylic emulsion, 4~8 parts of modified surface active's agent, 10~15 parts of curing agent and foaming agent.Preparation method：1) polyethylene glycol, silicone acrylic emulsion and glass bead are mixed, obtains mixture A；2) after mixing phenol-formaldehyde resin modified and phenolic resin fluidity improver, 50~60 DEG C is warming up to, mixture A, curing agent and toughener is added, mixture B is obtained；3) mixture B, modified surface active's agent and foaming agent are mixed evenly, are quickly poured into the mould of preheating and foam, after solidification and curing.The warming plate can avoid scaling-off problem, have the advantages that high intensity, good toughness and thermal conductivity factor are low.
Description
Technical field
The invention belongs to insulation material technical field, and in particular to a kind of plasticizing phenol formaldehyde warming plate and its preparation side
Method.
Background technology
Phenolic-aldehyde heat-insulation board and hard polyurethane foam belong to organic thermosetting thermal insulation material together, especially building energy saving rate in recent years
Gradually step up, using insulation material technical performance more and more higher, market demand is increasing.In Application in Building insulation material
In, not only require that physical technique performance is high and it is necessary to reach fire protecting performance.Foam and gather that phenol-formaldehyde resin modified is produced
Though urethane, which is hard bubbled, belongs to relatively good insulation material, excellent, shortcoming that two class insulation materials are had nothing in common with each other, without fine comprehensive
Technical performance.The hard polyurethane foam of polyurethane resin synthesis, with lightweight, low high-strength, thermal conductivity factor, good toughness and easy construction
The features such as, but fire protecting performance only up to reach that B1 grades of fire protecting performances, oxygen index (OI) only up to reach 30%.
The phenolic-aldehyde heat-insulation board of phenolic resin production, possesses the main principal advantages of Polyurethane Thermal Insulation Building Materials, but fire line
It can be protruded than hard polyurethane foam, fire resisting combustion is penetrated, high temperature resistant, low cigarette, oxygen index (OI) is up to 50%, but phenolic-aldehyde heat-insulation board and polyurethane
Hard bubble and compare, the maximum shortcoming of phenolic-aldehyde heat-insulation board is that fragility is big, acid big.Because the fragility of phenolic-aldehyde heat-insulation board is big, phenolic aldehyde heat preserving
Plate has that dry linting, elastic low, compressive strength are low when in use, and the problems such as thermal conductivity factor is not up to standard, intrinsic excellent fire protecting performance does not have
It can very well be utilized, therefore, influence the extension of the products application technology, while bringing many inconvenience to transport, construction.Especially
Pull strength is low, is difficult to meet relevant criterion requirement.Due to acid big so that phenolic-aldehyde heat-insulation board connects with metal, cement-based material
Touch and have certain corrosivity.
On July 4th, 2012, Chinese invention patent application publication No. CN102533015 A, disclosed a kind of external wall outer insulation
The preparation method of phenolic foam board fire protection flame retarding interfacial agents, it is, using vinyl acetate-ethylene copolymerization emulsions as base-material, to gather
Ammonium phosphate is dehydration catalyst, pentaerythrite is carbon forming agent and melamine is the flame-retardant system of foaming agent, and adds other and help
Agent is formulated.The technical scheme is base-material due to vinyl acetate-ethylene copolymerization emulsions using aqua type, although normal
Temperature can increase the toughness of insulation phenol formaldehyde foam plate surface；But the heat decomposition temperature of vinyl acetate-ethylene copolymerization emulsions compared with
It is low, about 230 DEG C or so；Run into that high temp fire bakes its viscosity and toughness rapidly disappears, directly contribute coming off for coating material.Cause
This, the fire protection flame retarding interfacial agents using effect is not good.
The content of the invention
The present invention proposes a kind of plasticizing phenol formaldehyde warming plate, and the warming plate can avoid scaling-off problem, and with strong
Spend height, good fire protecting performance, good toughness and the low advantage of thermal conductivity factor.
The technical proposal of the invention is realized in this way：
A kind of plasticizing phenol formaldehyde warming plate, is calculated by weight, including following raw material：
50~70 parts of phenol-formaldehyde resin modified, 15~25 parts of glass bead, 1~3 part of phenolic resin fluidity improver, toughness reinforcing
4~8 parts of agent, 4~8 parts of polyethylene glycol, 3~6 parts of silicone acrylic emulsion, 4~8 parts of modified surface active's agent, 10~15 parts of curing agent with
And 4~8 parts of foaming agent；Wherein, the phenol-formaldehyde resin modified is nonyl phenolic phenolic resin and polyamide modified phenolic resin, institute
Modified surface active's agent is stated to be made up of tween, castor oil polyoxyethylene ether and fluorocarbon surfactant.
Preferably, the content of the polyamide modified phenolic resin in the phenol-formaldehyde resin modified is 20~30wt%, nonyl
The content of phenolic phenolic resin is 70~80wt%.
Preferably, one kind in ethylene bis stearic acid amide, monoglyceride of the phenolic resin fluidity improver or
Two kinds.
Preferably, toughener is the mixture of modified silica fibre and terminal hydroxy group polybutadiene.
Preferably, the foaming agent is petroleum ether or pentane, and the curing agent is phosphoric acid, p-methyl benzenesulfonic acid or salt
Acid.
It is a further object to provide a kind of preparation method of plasticizing phenol formaldehyde warming plate, including following step
Suddenly：
1) polyethylene glycol, silicone acrylic emulsion and glass bead are mixed evenly, obtain mixture A；
2) after mixing phenol-formaldehyde resin modified and phenolic resin fluidity improver, 50~60 DEG C are warming up to, then add
Enter mixture A, curing agent and toughener, stir, obtain mixture B；
3) mixture B, modified surface active's agent and foaming agent are mixed evenly, are quickly poured into the mould of preheating
After foaming, solidification and curing.
Preferably, one kind in ethylene bis stearic acid amide, monoglyceride of the phenolic resin fluidity improver or
Two kinds.
Preferably, the preheating temperature of preheated mold is 60~70 DEG C.
Toughener is preferentially modified the mixture of silica fibre and terminal hydroxy group polybutadiene, because modified silica fibre and hydroxyl end
Base polybutadiene cooperates with the toughness of increase phenolic foam board with glass bead.
Beneficial effects of the present invention：
1st, phenolic resin is substituted with polyamide modified phenolic resin using nonyl phenolic phenolic resin in the present invention, wherein few
Polyamide modified phenolic resin is measured (no more than 30wt%, otherwise to run counter to desire, it is impossible to play polyamide modified phenolic resin energy
Enough improve the effect of the mobility of phenolic resin) the network compactness of phenolic resin can be effectively reduced, improve the fragility of foam,
It is promoted to flow, so as to improve its toughness.
2nd, can using the modified surface active's agent being made up of tween, castor oil polyoxyethylene ether and fluorocarbon surfactant
With the rate of closed hole difference and the poor defect of foaming characteristic for overcoming union base phenolic phenolic resin to bring, rate of closed hole is significantly improved, is reduced
Thermal conductivity factor.
3rd, glass bead is dispersed in polyethylene glycol in silicone acrylic emulsion by the present invention, and portion envelops are carried out to glass bead,
Its amalgamation in phenolic resin is improved, under the promotion of phenolic resin fluidity improver, toughness reinforcing is dispersed in
In phenolic resin warming plate, it is to avoid scaling-off problem occur, fire protecting performance is high.
3rd, the thermal conductivity factor of plasticizing phenol formaldehyde warming plate of the invention is 0.022~0.026W/mK, and compressive strength is
0.272~0295MPa, compression strength is 0.22~0.24MPa, and oxygen index (OI) is 45~50.
Embodiment
Embodiment 1
A kind of plasticizing phenol formaldehyde warming plate, is calculated by weight, including following raw material：
60 parts of phenol-formaldehyde resin modified, 20 parts of glass bead, 2 parts of ethylene bis stearic acid amide, 6 parts of toughener, polyethylene glycol 4
6 parts of~8 parts, 3~6 parts of silicone acrylic emulsion, 6 parts of modified surface active's agent, 2 parts of phosphatase 11 and petroleum ether.Phenol-formaldehyde resin modified is
75wt% nonyl phenolic phenolic resin and the polyamide modified phenolic resin of 25wt%, modified surface active's agent is by tween, castor oil
APEO is constituted with fluorocarbon surfactant.Toughener is the mixture of modified silica fibre and terminal hydroxy group polybutadiene.
Preparation method：
1) polyethylene glycol, silicone acrylic emulsion and glass bead are mixed evenly, obtain mixture A；
2) after mixing phenol-formaldehyde resin modified and ethylene bis stearic acid amide, 55 DEG C is warming up to, mixture is added
A, phosphoric acid and toughener, stir, and obtain mixture B；
3) mixture B, modified surface active's agent and petroleum ether are mixed evenly, it is 65 to be quickly poured into preheating temperature
DEG C mould in foam, solidification.
Embodiment 2
A kind of plasticizing phenol formaldehyde warming plate, is calculated by weight, including following raw material：
50 parts of phenol-formaldehyde resin modified, 15 parts of glass bead, 1 part of monoglyceride, 4 parts of toughener, 4 parts of polyethylene glycol, the breast of silicon third
4 parts of 6 parts of liquid, 4 parts of modified surface active's agent, 10 parts of p-methyl benzenesulfonic acid and pentane.Phenol-formaldehyde resin modified is 80wt% nonyls
Phenolic phenolic resin and the polyamide modified phenolic resin of 20wt%, modified surface active's agent is by tween, castor oil polyoxyethylene ether
Constituted with fluorocarbon surfactant.Toughener is the mixture of modified silica fibre and terminal hydroxy group polybutadiene.
Preparation method：
1) polyethylene glycol, silicone acrylic emulsion and glass bead are mixed evenly, obtain mixture A；
2) after mixing phenol-formaldehyde resin modified and monoglyceride, 60 DEG C is warming up to, mixture A is added, to toluene sulphur
Acid and toughener, stir, obtain mixture B；
3) mixture B, modified surface active's agent and pentane are mixed evenly, it is 60 to be quickly poured into preheating temperature
DEG C mould in foam, solidification.
Embodiment 3
A kind of plasticizing phenol formaldehyde warming plate, is calculated by weight, including following raw material：
70 parts of phenol-formaldehyde resin modified, 25 parts of glass bead, 25 parts of ethylene bis stearic acid amide, 8 parts of toughener, modified surface
8 parts of 8 parts of activating agent, 8 parts of polyethylene glycol, 3 parts of silicone acrylic emulsion, 15 parts of hydrochloric acid and pentane.Phenol-formaldehyde resin modified is 70wt%
Nonyl phenolic phenolic resin and the polyamide modified phenolic resin of 30wt%, modified surface active's agent is by tween, castor oil polyoxy second
Alkene ether is constituted with fluorocarbon surfactant.Toughener is the mixture of modified silica fibre and terminal hydroxy group polybutadiene.
Preparation method：
1) polyethylene glycol, silicone acrylic emulsion and glass bead are mixed evenly, obtain mixture A；
2) after mixing phenol-formaldehyde resin modified and ethylene bis stearic acid amide, 50 DEG C is warming up to, mixture is added
A, hydrochloric acid and toughener, stir, and obtain mixture B；
3) mixture B, modified surface active's agent and pentane are mixed evenly, it is 70 to be quickly poured into preheating temperature
DEG C mould in foam, solidification.
Test example
The warming plate that embodiment 1-3 is prepared carries out performance detection, the results are shown in Table 1.
The embodiment 1-3 warming plate performance test results of table 1
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (7)
1. a kind of plasticizing phenol formaldehyde warming plate, it is characterised in that calculate by weight, including following raw material：
50~70 parts of phenol-formaldehyde resin modified, 15~25 parts of glass bead, 1~3 part of phenolic resin fluidity improver, toughener 4
~8 parts, 4~8 parts of polyethylene glycol, 3~6 parts of silicone acrylic emulsion, 4~8 parts of modified surface active's agent, 10~15 parts of curing agent and hair
4~8 parts of infusion；Wherein, the phenol-formaldehyde resin modified is nonyl phenolic phenolic resin and polyamide modified phenolic resin, described to change
Property surfactant is made up of tween, castor oil polyoxyethylene ether and fluorocarbon surfactant.
2. plasticizing phenol formaldehyde warming plate according to claim 1, it is characterised in that the phenolic resin liquidity costs
The one kind or two kinds of agent in ethylene bis stearic acid amide, monoglyceride.
3. plasticizing phenol formaldehyde warming plate according to claim 1 or 2, it is characterised in that toughener is modified silica fibre
With the mixture of terminal hydroxy group polybutadiene.
4. plasticizing phenol formaldehyde warming plate according to claim 1 or 2, it is characterised in that the foaming agent is petroleum ether
Or pentane, the curing agent is phosphoric acid, p-methyl benzenesulfonic acid or hydrochloric acid.
5. the preparation method of plasticizing phenol formaldehyde warming plate as claimed in claim 1, it is characterised in that comprise the following steps：
1) polyethylene glycol, silicone acrylic emulsion and glass bead are mixed evenly, obtain mixture A；
2) after mixing phenol-formaldehyde resin modified and phenolic resin fluidity improver, 50~60 DEG C is warming up to, is added mixed
Compound A, curing agent and toughener, stir, and obtain mixture B；
3) mixture B, modified surface active's agent and foaming agent are mixed evenly, are quickly poured into the mould of preheating and send out
After bubble, solidification and curing.
6. the preparation method of plasticizing phenol formaldehyde warming plate according to claim 5, it is characterised in that the phenolic resin
The one kind or two kinds of fluidity improver in ethylene bis stearic acid amide, monoglyceride.
7. the preparation method of plasticizing phenol formaldehyde warming plate according to claim 5, it is characterised in that preheated mold it is pre-
Hot temperature is 60~70 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710587253.7A CN107325479A (en) | 2017-07-18 | 2017-07-18 | Plasticizing phenol formaldehyde warming plate and preparation method thereof |
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| CN201710587253.7A CN107325479A (en) | 2017-07-18 | 2017-07-18 | Plasticizing phenol formaldehyde warming plate and preparation method thereof |
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| CN107266853A (en) * | 2017-07-18 | 2017-10-20 | 合肥广能新材料科技有限公司 | Phenolic foam heat insulation plate and preparation method thereof |
| CN107446305A (en) * | 2017-07-18 | 2017-12-08 | 合肥广能新材料科技有限公司 | Phenolic resin warming plate and preparation method thereof |
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2017
- 2017-07-18 CN CN201710587253.7A patent/CN107325479A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834136A (en) * | 2012-11-22 | 2014-06-04 | 合肥杰事杰新材料股份有限公司 | Toughened modified phenolic resin foam material and its preparation method |
| CN103723950A (en) * | 2013-12-12 | 2014-04-16 | 青岛无为保温材料有限公司 | Novel composite insulation slurry and preparation method thereof |
| CN104072941A (en) * | 2014-07-18 | 2014-10-01 | 锦州市好为尔保温材料有限公司 | Nano modified phenolic aldehyde foam insulation board and preparation method thereof |
| CN104356591A (en) * | 2014-11-06 | 2015-02-18 | 聊城大学 | Toughened enhanced phenolic foam insulation material and preparation method thereof |
| CN106554598A (en) * | 2016-11-09 | 2017-04-05 | 郑州圣莱特空心微珠新材料有限公司 | A kind of phenolic resin warming plate and preparation method thereof |
| CN107266853A (en) * | 2017-07-18 | 2017-10-20 | 合肥广能新材料科技有限公司 | Phenolic foam heat insulation plate and preparation method thereof |
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