CN103694626B - A kind of phenolic foams - Google Patents

A kind of phenolic foams Download PDF

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Publication number
CN103694626B
CN103694626B CN201310701685.8A CN201310701685A CN103694626B CN 103694626 B CN103694626 B CN 103694626B CN 201310701685 A CN201310701685 A CN 201310701685A CN 103694626 B CN103694626 B CN 103694626B
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acid
phenolic
foams
floating bead
phenolic resin
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CN103694626A (en
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邓刚
彭绵广
焦壮
秦海洋
乔林
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Shandong Shengquan New Material Co Ltd
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Shandong Shengquan New Material Co Ltd
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Abstract

The present invention relates to a kind of energy-saving building materials, it is specifically related to a kind of phenolic foams, prepared by foaming and solidify by phenolic resin, surfactant, toughener, stabilizer, foaming agent and acid catalyst, it is characterized in that described stabilizer is floating bead, addition is the 1.5%-10% of phenolic foams mass fraction.Present invention solves the technical problem that and there are provided a kind of phenolic foam material, this phenolic foam material tensile strength is high, good stability of the dimension, and also solves sheet material and be heated the problem of easy warpage.

Description

A kind of phenolic foams
Technical field
The present invention relates to a kind of energy-saving building materials, be specifically related to a kind of phenolic foams.
Background technology
Phenol formaldehyde foam have the laudatory title of " king of insulation material ", is a new generation's insulated fire deadener.Phenolic foam material belongs to the organic hard aluminium foil froth pulp of macromolecule, is formed by thermosetting phenolic resin foaming.It has lightweight, fire prevention, chance naked light do not burn, smokeless, nontoxic, without dripping off, use temperature range wide (-196~+200 DEG C), do not shrink under low temperature environment, not brittle feature.
But traditional phenolic foam board dimensional stability is bad, and intensity is bad, plate face is heated and warpage easily occurs.The reinforcing material adopted in the world at present for this problem mainly has two kinds: one is glass fibre or fiberglass braided thing, the addition of this material, the intensity index of polyurethane foam plastics can be improved significantly, but the increase along with fibre weight, the density of foams also increases significantly, and, use this enhancement method, technique is more complicated, it is very difficult to obtain reproducible goods;Another kind is hollow glass micropearl, adopts hollow glass micropearl as reinforcing material, it is possible to extremely efficient to increase comprcssive strength and the dimensional stability of goods, and the density of foams is without obvious increase.But, the source of glass microballoon and price (22000 yuan/t) make the practicality of this method be restricted.
Such as " chemical industry mineral and processing " the 21st page that the 6th phase in 2004 publishes, effectively solve this problem, have employed the hollow float bead reinforcing material as polyurethane foam plastics.Hollow float bead is a kind of microballon separated from the flyash in thermal power plant, and it has aboundresources, density little, cheap (180 yuan/t), the feature such as easy to use.Adopt hollow float bead as strengthening phase, not only foamed materials is had obvious reinforced effects, and the anti-flammability of goods can be improved.Experiment proves, its application can improve comprcssive strength and the dimensional stability of goods significantly, is a kind of practicable reinforcement.But the method uses floating bead more, and when sheet material is heated, the problem that there is also the easy warpage of sheet material.
Summary of the invention
Present invention solves the technical problem that and there are provided a kind of phenolic foam material, this phenolic foam material tensile strength is high, good stability of the dimension, and also solves sheet material and be heated the problem of easy warpage.
A kind of phenolic foams, is prepared by foaming and solidify by phenolic resin, surfactant, toughener, stabilizer, foaming agent and acid catalyst, it is characterised in that described stabilizer is floating bead, and addition is the 1.5%-2.5% of phenolic foams mass fraction.
With the ultrasonic 1-2h of ultrasonic activation instrument after pretreated floating bead is mixed with phenolic resin, then with other raw material mixed processing.
Described floating bead first and uses the ultrasonic 1-2h of ultrasonic activation instrument after phenolic resin mixing.
Described phenolic resin is the water absorption rate phenolic resin less than 2%.
Described surfactant is one or more in polysiloxanes, polyoxyethylene ether, polyoxypropylene, Pluronic F68, polyethylene sorbitan fatty acid esters and Polysorbate.
Described toughener is one or more in ethylene glycol, polyethylene glycol 200, PEG400, polyethylene glycol-800, cetomacrogol 1000, polyvinyl alcohol, PEPA and nitrile rubber.
Described acid as curing agent is the mixture of acid and alcohol.
Described acid is one or more in hydrochloric acid, sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, benzenesulfonic acid, phenolsulfonic acid.
Described blowing temperature is 60-90 DEG C.
Excessive floating bead increases the density of phenol formaldehyde foam, has certain steric effect in the cross-linked polymeric of phenol formaldehyde foam so that the degree of cross linking of phenol formaldehyde foam is abundant not, therefore can not reach significantly high intensity and good stability;Through the floating bead that methacrylate-chromic chloride processes, being provided that functional group realizes crosslinking with phenol formaldehyde foam, therefore intensity, heat conduction, water suction aspect are all significantly improved.
Beneficial effect:
1, tensile strength is high, good stability of the dimension;
2, efficiently solve sheet material to be heated the problem of easy warpage.
Detailed description of the invention:
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but it is to be understood that these describe to be intended merely to and further illustrate the features and advantages of the present invention, rather than limiting to the claimed invention.In embodiment, phenolic resin used is low water absorption phenolic resin, and water absorption rate is less than 2%.
Embodiment 1
By the phenolic resin of 100 mass parts and 8 mass parts normal hexane foaming agent, 6 mass parts silicone emulsifiers, 8 mass parts epoxy resin tougheners, 25 mass parts acid as curing agent (xylene monosulfonic acid: glycerol: water=6:3:1) and floating bead mix homogeneously that 2.3 mass parts particle diameters are 120 microns, it is quickly poured into foaming in the mould that preheating is 70 DEG C, solidify 30min at 70 DEG C, prepare phenol formaldehyde foam.
Embodiment 2
By the phenolic resin of 100 mass parts and 9 mass parts pentane foaming agent, 6 mass parts polyoxypropylene emulsifying agents, 8 mass parts polyethylene glycol 200 toughener, 24 mass parts acid as curing agent (p-methyl benzenesulfonic acid: glycerol: water=7:2:1) and floating bead mix homogeneously that 3.6 mass parts particle diameters are 120 microns, it is quickly poured into foaming in the mould that preheating is 70 DEG C, solidify 30min at 80 DEG C, prepare phenol formaldehyde foam.
Embodiment 3
By the phenolic resin of 100 mass parts and 8 mass parts petroleum ether foaming agent, 7 mass parts polysiloxanes and the mixture emulsifier of polyethylene sorbitan fatty acid esters, 9 mass parts ethylene glycol and the mixture toughener of PEPA, 25 mass parts acid as curing agent (phosphoric acid: glycerol: water=7:2:1) and floating bead mix homogeneously that 1.3 mass parts particle diameters are 120 microns, be quickly poured into preheating be 70 DEG C mould in foaming, solidify 30min at 85 DEG C, prepare phenol formaldehyde foam.
Embodiment 4
By the phenolic resin of 100 mass parts and 8 mass parts petroleum ether foaming agent, 7 mass parts polysiloxanes and the mixture emulsifier of polyethylene sorbitan fatty acid esters, 9 mass parts ethylene glycol and the mixture toughener of PEPA, 25 mass parts acid as curing agent (phosphoric acid: glycerol: water=7:2:1) and floating bead mix homogeneously that 5 mass parts particle diameters are 120 microns, be quickly poured into preheating be 70 DEG C mould in foaming, solidify 30min at 85 DEG C, prepare phenol formaldehyde foam.
Embodiment 5
First with methacrylate-chromic chloride, floating bead is carried out pretreatment, again by the phenolic resin of 100 mass parts and floating bead mix homogeneously that 1.9 mass parts particle diameters are 100 microns, add the mixture of 8 mass parts pentane foaming agent, 6 mass parts polysiloxanes and polyoxypropylene as surfactant, 8 mass parts ethylene glycol 1000 toughener and 25 mass parts acid as curing agent (xylene monosulfonic acid: glycerol: water=7:2:1) mix homogeneously, mixture is quickly poured into foaming in the mould that preheating is 70 DEG C, solidify 30min at 75 DEG C, prepare phenol formaldehyde foam.
Embodiment 6
First with methacrylate-chromic chloride, floating bead is carried out pretreatment, again by the phenolic resin of 100 mass parts and floating bead ultrasonic 2h mix homogeneously under ultrasound wave that 2 mass parts particle diameters are 100 microns, add the mixture of 8 mass parts pentane foaming agent, 6 mass parts polysiloxanes and polyoxypropylene as surfactant, 8 mass parts ethylene glycol 1000 toughener and 25 mass parts acid as curing agent (xylene monosulfonic acid: glycerol: water=7:2:1) mix homogeneously, mixture is quickly poured into foaming in the mould that preheating is 70 DEG C, solidify 30min at 75 DEG C, prepare phenol formaldehyde foam.
Phenol formaldehyde foam obtained by embodiment detects successively by the following method
1. the mensuration of density
It is measured by the method for GB/T6343-2009
2. the mensuration of heat conductivity
Measure by the method for GB/T10294-2008 or 10295-2008
3. the mensuration of water absorption rate
Measure by the method for GB/T8810-2005
4. the mensuration of dimensional stability
Measure by the method for GB/T8811-2008
5. it is perpendicular to the mensuration of the tensile strength in direction, plate face
The tensile strength test method being perpendicular to direction, plate face by JG149-2003 Appendix D measures
6. the mensuration of combustibility
By GB/T8624-2007, GB/T20284-2006 or GB/T8624-1997 the 5.1st the method for clause be measured
Oxygen index (OI) is more high, and fire resistance is more good.
The performance data of phenolic foam board in embodiment
Density (kg/m3) Compressive strength (Mpa) It is perpendicular to the tensile strength (Mpa) in direction, plate face Water absorption rate (%) Heat conductivity W/(m k) Dimensional stability (%) Oxygen index (OI) (%)
Embodiment 1 51.5 0.22 0.11 1.0 0.020 1.2 53
Embodiment 2 50.4 0.21 0.11 1.2 0.024 1.2 52
Embodiment 3 51.2 0.16 0.10 2.0 0.038 1.4 45
Embodiment 4 51.4 0.22 0.11 1.0 0.020 1.1 60
Embodiment 5 51.8 0.22 0.11 0.9 0.023 0.9 63
Embodiment 6 51.9 0.23 0.11 0.9 0.023 1.0 65
Data analysis: from dimensional stability, the 1.5-2.5 dimensional stability effect that floating bead addition is phenolic foams gross mass has reached the addition more effect of floating bead amount, when floating bead addition is less than the 1.5% of phenolic foams gross mass, dimensional stability, fire-retardant coefficient etc. all significantly lower;When adopting after first by phenolic resin and floating bead mixing, the method adding foaming agent, surfactant, toughener and firming agent mix homogeneously, the dimensional stability of phenolic foams is improved significantly, and after especially first floating bead methacrylate-chromic chloride being carried out pretreatment, effect becomes apparent from;After floating bead methacrylate-chromic chloride is carried out pretreatment, then the effect that the floating bead after phenolic resin and process mixes in ultrasonic instrument is become apparent from.Floating bead microsphere well can merge with phenolic aldehyde, himself is hole-closing structure, reduces thermal convection current, and again because it is the thin hollow of wall, heat is only small from the thermal conduction effect hole wall, and therefore microsphere has good heat insulation effect.

Claims (6)

1. a phenolic foams, is prepared by foaming and solidify by phenolic resin, surfactant, toughener, stabilizer, foaming agent and acid as curing agent, it is characterised in that described stabilizer is floating bead, and addition is the 1.5%-2.5% of phenolic foams mass fraction;
Before described floating bead mixes with phenolic resin, first with methacrylate-chromic chloride, floating bead is carried out pretreatment, then dry;
With the ultrasonic 1-2h of ultrasonic activation instrument after pretreated floating bead is mixed with phenolic resin, then with other raw material mixed processing;
Described phenolic resin is the water absorption rate phenolic resin less than 2%.
2. phenolic foams according to claim 1, it is characterized in that, described surfactant is one or more in polysiloxanes, polyoxyethylene ether, polyoxypropylene, Pluronic F68, polyethylene sorbitan fatty acid esters and Polysorbate.
3. phenolic foams according to claim 1, it is characterized in that, described toughener is one or more in ethylene glycol, polyethylene glycol 200, PEG400, polyethylene glycol-800, cetomacrogol 1000, polyvinyl alcohol, PEPA and nitrile rubber.
4. phenolic foams according to claim 1, it is characterised in that described acid as curing agent is the mixture of acid and alcohol.
5. phenolic foams according to claim 4, it is characterised in that described acid is one or more in hydrochloric acid, sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, benzenesulfonic acid, phenolsulfonic acid.
6. phenolic foams according to claim 1, it is characterised in that blowing temperature is 60-90 DEG C.
CN201310701685.8A 2013-12-19 2013-12-19 A kind of phenolic foams Active CN103694626B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107415030A (en) * 2017-07-27 2017-12-01 巢湖市荣达塑业有限公司 A kind of washing machine counter weight with heat-insulating property makes mould
CN107286568A (en) * 2017-08-01 2017-10-24 方碧水 A kind of phenol formaldehyde foam and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
抗事故包装箱用酚醛泡沫制备及其性能评价;马晓雄等;《工程塑料应用》;20080710;第36卷(第7期);第60-63页 *

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