CN104262898B - A kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam - Google Patents

A kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam Download PDF

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CN104262898B
CN104262898B CN201410462630.0A CN201410462630A CN104262898B CN 104262898 B CN104262898 B CN 104262898B CN 201410462630 A CN201410462630 A CN 201410462630A CN 104262898 B CN104262898 B CN 104262898B
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foam
phenol formaldehyde
phenol
carbamide
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CN104262898A (en
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李效玉
叶俊
邱藤
段红云
张鑫
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention discloses a kind of organo-mineral complexing modified flame-retardant phenol formaldehyde foam, thermosetting phenolic resin by formaldehyde, phenol, organic modifiers synthesis modification in the basic conditions, then after vacuum dehydration to certain viscosity, add surfactant, foaming agent, firming agent, inorganic modifier, stir and foam.Wherein organic modifiers is the polyfunctionality glycidyl ether of long-chain, it can improve the fragility of tradition phenol formaldehyde foam, and that reduces foam falls slag rate, and inorganic modifier is the nano imvite of carbamide intercalation, while reinforcement organically-modified phenol formaldehyde foam anti-flammability, improve the physical and mechanical properties of foam.The method modified by this organo-mineral complexing finally gives good mechanical performance, falls the phenol formaldehyde foam that slag rate is low, fire resistance is good.

Description

A kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam
Technical field
The present invention relates to a kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam, be mainly used in external wall Insulation.
Background technology
Phenolic resin is one of the most industrialized resin.Phenolic resin synthesis the earliest can trace back to 20 Beginning of the century, from Belgian chemist L.H.bankcland first time novolak resin in the lab, And the synthesis mechanism of phenolic resin has been carried out preliminary parsing and research.The fifties in last century, phenolic aldehyde tree Fat the most in West Europe, North America, Japan Area use widely.Phenolic resin because of its good insulating properties, The advantage such as thermal insulation, high intensity is widely used in multiple industry, specifically include that heat preserving and insulating material, The manufacture of wood-based plate, fire-proof and thermal-insulation coating, high abrasion plastic product etc..
In recent years, flourish along with China's building trade, many urban architectures were due to exterior-wall heat insulation material Material flame retardant rating is the most up to standard, causes fire to occur, causes a tremendous loss of lives.2009 and state in 2011 " outer heat preservation system and the decoration of exterior wall fire prevention temporary provisions " that family issues (lead to word [No. 2009146] and " enter by public affairs One step clear and definite civil buildings heat insulating material for external fire supervision management is about the notice required " (public affairs disappear [2011165 Number]), the fire resistance of building materials is proposed strict requirements, the leading indicator oxygen index (OI) OI index < of material 22 is combustible material, and 22 < OI index < 27 are combustible materials, and OI index > 28 is nonflammable material, and OI refers to Counting more than 32 is B1Level flame-retardant thermal insulation material, phenol formaldehyde foam reaches B1Level fire retardant foam standard, with Time its cheap, synthesis technique simple, in terms of building materials insulation material, have irreplaceable status. But the phenyl ring of rigid structure occupies substantial amounts of ratio in phenol formaldehyde foam, phenyl ring is piled up connection in a large number and is caused The shortcoming that phenol formaldehyde foam poor toughness, pulverization rate are high limits the development of phenol formaldehyde foam.
The modification of phenolic resin mainly has physical modification and chemical modification two kinds, and wherein physical modification is mainly Various elastic high, the high liquid good with resin compatible of modulus, powder, undulation degree is added in resin Material, reaches enhancing, toughness reinforcing purpose, but all has a significant impact the fire resistance of foam.Chemistry changes Property be broadly divided into two big classes: one is to replace part phenol to react with formaldehyde with various phenolic compounds, Phenolic compound with particular characteristic can be linked among phenolic resin, to phenol in chemical constitution Urea formaldehyde is modified, but due to the existence of phenyl ring in phenolic compound, toughening effect is inconspicuous.Two are The compound with soft segment and phenol, formaldehyde copolymer is allowed to carry out synthesis modification phenolic resin.Liang Mingli etc. People uses base polyurethane prepolymer for use as and phenol formaldehyde foam to carry out chemical reaction, allows the soft segment of polyurethane be linked into Among phenol formaldehyde foam, the addition of a small amount of performed polymer can be greatly lowered the pulverization rate of foam, but this use Polyurethane-modified foam oxygen index (OI) can drastically decline.Within 2005, first Yang.H synthesizes a kind of phosphorous height The polyether compound of molecular weight, then uses this compound to be modified phenol formaldehyde foam, steeps at phenolic aldehyde Foam introduces phosphorous group and improves the oxygen index (OI) of modified foam.The foam oxygen index (OI) finally given has necessarily The rise of degree, reaches B1The demand of level fire retardant foam, but this method of modifying cost is the highest, difficult With popularization and application.
Summary of the invention
The invention discloses a kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam, by formaldehyde, phenol, The thermosetting phenolic resin of organic modifiers synthesis modification in the basic conditions, then through vacuum dehydration to one After determining viscosity, add surfactant, foaming agent, firming agent, inorganic modifier, stir and carry out Foaming.Wherein organic modifiers is the polyfunctionality glycidyl ether of long-chain, and it can improve tradition phenolic aldehyde The fragility of foam, that reduces foam falls slag rate, and inorganic modifier is the nano imvite of carbamide intercalation, While reinforcement organically-modified phenol formaldehyde foam anti-flammability, improve the physical and mechanical properties of foam.By this The modified method of Organic-inorganic composite finally gives good mechanical performance, falls that slag rate is low, fire resistance good Phenol formaldehyde foam.
A kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam, it is characterised in that: after including dehydration, viscosity is Matrix resin 100 weight portion of 4000-6000mpa.s, surfactant 5 weight portion, foaming agent 5 weight Amount part, firming agent 10 weight portion, inorganic modifier 0-10 weight portion, after mechanical agitation is uniform, fall Enter in mould, foam 3 hours at 70 DEG C;Surfactant is Tween 80;Foaming agent is pentane; Firming agent is phosphoric acid;Inorganic modifier is carbamide intercalated montmorillonite;
Wherein matrix resin includes phenol, formaldehyde, polyfunctionality glycidyl ether, base catalyst;Its Middle phenol 100 weight portion, mass percent are the formalin of 37%: 130-170 weight portion, many Degree of functionality glycidyl ether: 3-10 weight portion, base catalyst are 30wt% sodium hydrate aqueous solution: 8-15 Weight portion.
Polyfunctionality glycidyl ether be polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, Ethylene glycol diglycidyl ether, 1,4-Ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl glycerin ether, 1,6- Hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, glycerin triglycidyl ether it One.
Inorganic modifier is carbamide intercalated montmorillonite, and preparation method is as follows: pulverize after being dried by carbamide, Obtain 200 mesh urea powder after sieving, then urea powder and montmorillonite powder are uniformly mixed, carbamide Addition is the 10-40% of montmorillonite weight portion, is finally put in 90 DEG C of baking ovens by finely dispersed mixture Activation 2h, obtains carbamide intercalated montmorillonite.
Described phenol formaldehyde foam preparation method is as follows:
1) when stirring, phenol 100 weight portion, mass percent be 37% formaldehyde water-soluble Liquid: 130-170 weight portion, base catalyst 30wt% sodium hydrate aqueous solution 8-15 weight portion, many officials Energy degree glycidyl ether 3-10 weight portion adds in reactor, and stir speed (S.S.) is 600r/min, is warming up to 60 DEG C Rear insulation reaction 30min;
2) it is warming up to 90-98 DEG C, cools down after insulation reaction 30-90min at this temperature;
3) obtain, after vacuum pump dehydration 60-120min, the modified matrix that viscosity is 4000-6000mpa.s Resin;
4) by modified matrix resin 100 weight portion, surfactant 5 weight portion, foaming agent 5 weight portion, Firming agent 10 weight portion, inorganic modifier 3-10 weight portion, after mechanical agitation is uniform, pour mould into In, at 70 DEG C, foaming obtains modified phenolic foam in 3 hours.
The present invention by the modified method of Organic-inorganic composite, is improving phenol formaldehyde foam fragility and to fall slag many Ensure its fire resistance simultaneously, control the cost of product simultaneously.
Accompanying drawing explanation
The montmorillonite sample XRD of Fig. 1 difference urea content characterizes
Along with being gradually increased of carbamide addition, 001 crystal face interlamellar spacing of montmorillonite is also gradually increased, and works as urine Element addition is to obtain maximum spacing during the 30% of montmorillonite weight portion.
Detailed description of the invention
Embodiment 1
Inorganic modifier is carbamide intercalated montmorillonite, and preparation method is as follows: use high speed powder after being dried by carbamide Broken machine is pulverized, and obtains 200 mesh urea powder, then by urea powder and montmorillonite powder after sieving Uniformly mixing under high speed dispersor, carbamide addition is the 10% of montmorillonite weight portion, finally will dispersion Uniform mixture puts into high-temperature activation 2h in 90 DEG C of baking ovens, obtains carbamide intercalated montmorillonite.
The preparation of phenol formaldehyde foam: when stirring, phenol 100 weight portion, mass percent are 37% Formalin: 130 weight portions, base catalyst 30wt% sodium hydrate aqueous solution 8 weight portion, Polyethyleneglycol diglycidylether: 3 weight portions add in reactor, and stir speed (S.S.) is 600r/min, heats up Insulation reaction 30min after 60 DEG C;It is warming up to 90 DEG C.Cool down after insulation reaction 30min at this temperature; The modified base that viscosity is 4000mpa.s is obtained after being dehydrated 60min with vacuum pump under-0.1MPa vacuum Body resin;Modified matrix resin 100 weight portion, surfactant 5 weight portion, foaming agent 5 weight portion, Firming agent 10 weight portion, inorganic modifier 3 weight portion, after mechanical agitation is uniform, pour in mould, At 70 DEG C, foaming obtains modified phenolic foam in 3 hours.
Embodiment 2
In the preparation method of present embodiment inorganic modifier carbamide intercalated montmorillonite, carbamide addition is de-for covering The 20% of soil addition, other are same as in Example 1.
Embodiment 3
In the preparation method of present embodiment inorganic modifier carbamide intercalated montmorillonite, carbamide addition is de-for covering The 30% of soil addition, other are same as in Example 1.
Embodiment 4
In the preparation method of present embodiment inorganic modifier carbamide intercalated montmorillonite, carbamide addition is de-for covering The 40% of soil addition, other are same as in Example 1.
Embodiment 5
In the preparation process of present embodiment phenol formaldehyde foam, formalin addition is 150 weight portions, its He is same as in Example 1.
Embodiment 6
In the preparation process of present embodiment phenol formaldehyde foam, formalin addition is 170 weight portions, its He is same as in Example 1.
Embodiment 7
In the preparation process of present embodiment phenol formaldehyde foam, 30wt% sodium hydrate aqueous solution addition is 12 weights Amount part, other are same as in Example 1.
Embodiment 8
In the preparation process of present embodiment phenol formaldehyde foam, 30wt% sodium hydrate aqueous solution addition is 15 Weight portion, other are same as in Example 1.
Embodiment 9
In the preparation process of present embodiment phenol formaldehyde foam, polyethyleneglycol diglycidylether addition is 6 weights Amount part, other are same as in Example 1.
Embodiment 10
In the preparation process of present embodiment phenol formaldehyde foam, polyethyleneglycol diglycidylether addition is 10 Weight portion, other are same as in Example 1.
Embodiment 11
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is polypropylene glycol two contracting Water glycerin ether, other are same as in Example 1.
Embodiment 12
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is that ethylene glycol bisthioglycolate shrinks Glycerin ether, other are same as in Example 1.
Embodiment 13
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is 1,4-ethylene glycol bisthioglycolate Glycidyl ether, other are same as in Example 1.
Embodiment 14
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is neopentyl glycol diglycidyl Glycerin ether, other are same as in Example 1.
Embodiment 15
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is 1,6-HD two Glycidyl ether, other are same as in Example 1.
Embodiment 16
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is trimethylolpropane Triglycidyl ether, other are same as in Example 1.
Embodiment 17
In the preparation process of present embodiment phenol formaldehyde foam, polyfunctionality glycidyl ether is glycerol three shrink Glycerin ether, other are same as in Example 1.
Embodiment 18
In the preparation process of present embodiment phenol formaldehyde foam, the second step reaction temperature of matrix resin is 95 DEG C, Other are same as in Example 1.
Embodiment 19
In the preparation process of present embodiment phenol formaldehyde foam, the second step reaction temperature of matrix resin is 98 DEG C, Other are same as in Example 1.
Embodiment 20
In the preparation process of present embodiment phenol formaldehyde foam, the second step response time of matrix resin is 60min, Other are same as in Example 1.
Embodiment 21
In the preparation process of present embodiment phenol formaldehyde foam, the second step reaction temperature of matrix resin is 90min, Other are same as in Example 1.
Embodiment 22
3rd step vacuum dehydration 90min of matrix resin in the preparation process of present embodiment phenol formaldehyde foam, Obtaining resin viscosity 5000mpa.s, other are same as in Example 1.
Embodiment 23
3rd step vacuum dehydration 120min of matrix resin in the preparation process of present embodiment phenol formaldehyde foam, Obtaining resin viscosity 6000mpa.s, other are same as in Example 1.
Embodiment 24
In the preparation process of present embodiment phenol formaldehyde foam, in foaming process, inorganic modifier addition is 6 weights Amount part, other are same as in Example 1.
Embodiment 25
In the preparation process of present embodiment phenol formaldehyde foam, in foaming process, inorganic modifier addition is 10 Weight portion, other are same as in Example 1.
Comparative example 1
Present embodiment is not added with polyfunctionality (+)-2,3-Epoxy-1-propanol in the preparation process of phenol formaldehyde foam in matrix resin Ether, is not added with inorganic modifier in foaming process, other are same as in Example 1.
Table 1 embodiment sample test performance

Claims (2)

1. an Organic-inorganic composite modified flame-retardant phenol formaldehyde foam, it is matrix resin 100 weight portion of 4000-6000mpa.s, surfactant 5 weight portion, foaming agent 5 weight portion, firming agent 10 weight portion, inorganic modifier 3-10 weight portion including viscosity after dehydration, after mechanical agitation is uniform, pour in mould, foam 3 hours at 70 DEG C;Surfactant is Tween 80;Foaming agent is pentane;Firming agent is phosphoric acid;Inorganic modifier is carbamide intercalated montmorillonite;
Wherein matrix resin includes phenol, formaldehyde, polyfunctionality glycidyl ether, base catalyst;Wherein phenol 100 weight portion, mass percent are the formalin of 37%: 130-170 weight portion, polyfunctionality glycidyl ether: 3-10 weight portion, base catalyst are 30wt% sodium hydrate aqueous solution: 8-15 weight portion;
It is characterized in that: inorganic modifier is carbamide intercalated montmorillonite, preparation method is as follows: pulverize after being dried by carbamide, 200 mesh urea powder are obtained after sieving, then urea powder and montmorillonite powder are uniformly mixed, carbamide addition is the 10-40% of montmorillonite weight portion, finally finely dispersed mixture is put into activation 2h in 90 DEG C of baking ovens, obtains carbamide intercalated montmorillonite.
Phenol formaldehyde foam the most according to claim 1, it is characterised in that preparation method is as follows:
1) when stirring, phenol 100 weight portion, mass percent are the formalin of 37%: 130-170 weight portion, base catalyst 30wt% sodium hydrate aqueous solution 8-15 weight portion, polyfunctionality glycidyl ether 3-10 weight portion add in reactor, stir speed (S.S.) is 600r/min, insulation reaction 30min after being warming up to 60 DEG C;
2) it is warming up to 90-98 DEG C, cools down after insulation reaction 30-90min at this temperature;
3) obtain, after vacuum pump dehydration 60-120min, the modified matrix resin that viscosity is 4000-6000mpa.s;
4) by modified matrix resin 100 weight portion, surfactant 5 weight portion, foaming agent 5 weight portion, firming agent 10 weight portion, inorganic modifier 3-10 weight portion, after mechanical agitation is uniform, pouring in mould, at 70 DEG C, foaming obtains modified phenolic foam in 3 hours.
CN201410462630.0A 2014-09-11 2014-09-11 A kind of Organic-inorganic composite modified flame-retardant phenol formaldehyde foam Active CN104262898B (en)

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CN106432653A (en) * 2016-08-30 2017-02-22 江苏德明新材料有限公司 Environment-friendly phenolic foam insulation board and preparation method thereof
CN106366560A (en) * 2016-08-30 2017-02-01 江苏德明新材料有限公司 Epoxy modified pressure-proof phenolic foam plate and preparation method thereof
CN107057288A (en) * 2017-05-22 2017-08-18 安徽三义和能源科技有限公司 A kind of preparation method of Pressure-resistant fireproof plate

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