CN105482357B - A kind of phenol resin composition and its expanded material and moulding material of preparation - Google Patents
A kind of phenol resin composition and its expanded material and moulding material of preparation Download PDFInfo
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Abstract
The present invention relates to a kind of phenol resin composition of polymeric material field and its expanded material and moulding material of preparation.The phenol resin composition of the present invention includes solid phenolic resin, Foaming of phenolic resin agent, expanded resin beads and nitrile rubber particle, and foaming base resin is resin of the heat distortion temperature higher than 90 DEG C under 0.45MPa loads wherein used by expanded resin beads.The expanded resin beads and nitrile rubber particle that the expanded material of the present invention includes the phenolic resin as matrix resin of crosslinked foaming and is dispersed therein, and be prepared by the phenol resin composition.The expanded material has low thermal conductivity factor and excellent fire resistance.Moulding material, which can be used as, made of the expanded material of the present invention meets the uses such as the incombustible insulation material of naked light, acoustic material, vibration-absorptive material, imitated wood material.
Description
Technical field
The present invention relates to polymeric material field, further, is related to a kind of phenol resin composition and its hair of preparation
Foam material and moulding material.
Background technology
Because building energy consumption is higher, in the case where present energy day is becoming tight, carrying out energy-saving heat preserving to building is
One necessary measure.
Phenolic aldehyde foam thermal insulation material good flame retardation effect, do not drip, do not burn under the conditions of naked light, without toxic and harmful gas
Release, that is, have meet naked light do not burn, be smokeless, nontoxic performance, but its fragility is big, easy efflorescence so that transport and construction are all
There is certain difficulty, limit its application.
The method used at present is by phenol formaldehyde foam and polystyrene foam composition composite foam material, prepares while has
There is the insulation material of the anti-flammability of phenolic aldehyde and the heat-insulating property of expanded polystyrene (EPS).At present in preparation process, the method for use
It is the compound vacuole that expanded polystyrene bead and liquid phenolic resin are mixed with to phenol formaldehyde foam and polystyrene foam composition
Foam material and corresponding sheet material.But the structure and preparation process due to resulting final sheet material is whard to control, makes
The application of this method is restricted, for example, the resin plate structure that this method obtains is uneven.Simultaneously because foaming polyphenyl
The storage life of ethene bead and liquid phenolic resin composition is short, limits expanded polystyrene bead and liquid phenolic resin group
The yield of compound, large batch of corresponding resin plate can not be produced, cause resin plate to be difficult to industrialized production.
The shortcomings that Publication No. GB2013209 (A) BP is in order to overcome final resin plate structure uneven, it is right
The component such as liquid phenolic resin and its curing agent and foaming agent has carried out strict regulation, makes the foaming or expanded of phenolic resin
Journey separates with its curing schedule, while the control in whole preparation process to the temperature of each step is very strict, so entirely
Preparation process heating process is complicated, and the restriction for temperature is very strict, but does not solve expanded polystyrene bead and liquid
The storage life of phenol resin composition is short, the shortcomings that can not producing corresponding resin plate in large quantity.
The present inventor is in order to comprehensively solve the above-mentioned problems in the prior art, in Chinese patent application
In CN102690494A phenolic resin/expanded resin beads composite wood is prepared for using solid phenolic resin and expanded resin beads
Material prepares the expanded material of even structure, fire resistance and excellent thermal insulation performance.Because phenolic resin uses solid-state phenolic aldehyde tree
Fat, and the heat distortion temperature of expanded resin beads used is higher, so prepared phenolic resin/expanded resin beads group
Compound does not have the problem of storage life is short, not influenceed by condition of cure yet.It can be used as and meet the incombustible acoustic material of naked light, subtract
Blanket, imitated wood material etc., it can especially be used as the incombustible insulation material of chance naked light of various highly effective and safes, such as
It can be used as incombustible, the safe heat preservation plate material of chance naked light of building trade.But prepared expanded material is still
In the presence of certain proportion it is larger the problem of.
The content of the invention
In order to solve the above-mentioned technical problem, the present inventor is preparing the mistake of phenolic resin/expanded resin beads composite
Foaming of phenolic resin agent and the nitrile rubber particle with cross-linked structure are added in journey simultaneously, in the expanded material for making gained
Phenolic resin is foamed with certain multiplying power, reduces the proportion of expanded material；Simultaneously because added in phenolic resin with friendship
It is coupled the nitrile rubber particle of structure, the abscess of foamed phenolic resin can be made more uniform and rate of closed hole is improved, finally
Further reduce the thermal conductivity factor of prepared expanded material.Expanded material obtained by institute's method described above not only has more
Excellent heat-insulating property and outstanding fire resistance, and solve common foamed phenolic resin closed pore in the prior art well
The problem of rate is small.This expanded material, which can be prepared, meets the shapings such as the incombustible acoustic material of naked light, vibration-absorptive material, imitated wood material
It material, can especially be used as the incombustible insulation material of chance naked light of various highly effective and safes, such as building can be used as
The heat preservation plate material that naked light is incombustible, safe of meeting of industry uses.
First purpose of the present invention is to provide a kind of phenol resin composition.
Second object of the present invention is to provide a kind of expanded material and preparation method thereof, and the expanded material is by the phenolic aldehyde
Resin combination is prepared, and has lower thermal conductivity factor, excellent fire resistance.
Third object of the present invention is to provide a kind of moulding material, is made by expanded material described above.The forming material
Material, which can be used as, meets the uses such as the incombustible insulation material of naked light, acoustic material, vibration-absorptive material, imitated wood material.
The phenol resin composition of the present invention, include the following components of blending：Solid phenolic resin, Foaming of phenolic resin
Agent, expanded resin beads and nitrile rubber particle.
The volume ratio of the solid phenolic resin and expanded resin beads is 5 ︰ 95~95 ︰ 5, preferably 5 ︰ 95~80 ︰ 20, more
It is preferred that the ︰ 60 of 5 ︰ 95~40.Wherein, in concrete practice, the implementation of the volume ratio is volume ratio as needed, will be above-mentioned
Weight required for calculating both components each according to the density of both components before component blending, take weight and obtain.
Described nitrile rubber particle is counted by 100 parts by weight of the solid phenolic resin, and its content is 0.5~95
Part, preferably 1~45 part, more preferably 1~30 part, further preferred 1~25 part.
The dosage of the Foaming of phenolic resin agent can be adjusted according to the expansion ratio of required solid phenolic resin.
(expansion ratio of the phenolic resin is normally controlled in 0.5~100 times, preferably 0.5~50 times, more preferably 0.5~20 times.) one
As counted by 100 parts by weight of the solid phenolic resin, its content be 0.5~50 part, preferably 1~30 part, more preferably 1~20
Part.
The solid phenolic resin in phenol resin composition of the present invention is the existing various solid-state phenolic aldehyde of prior art
Resin, it can be prepared by polycondensation phenol and aldehyde.The present invention is not limited the species of solid phenolic resin, can be thermosetting
Phenolic resin, or thermoplastic phenolic resin.
For the phenols for preparing the solid phenolic resin, there is no particular limitation, for example, can include it is following in it is any
It is a kind of：Phenol, orthoresol, metacresol, paracresol, o-ethyl phenol, m-ethylphenol, paraethyl phenol, o-propylphenol,
Propylphenol, n-propyl phenol, to sec-butyl phenol, p-t-butyl phenol, p-cyclohexylphenol, parachlorophenol, o-bromophenol,
Double (the 4 '-hydroxy benzenes of m -bromoacetophenone, p bromophenol, alpha-Naphthol, betanaphthol, resorcinol, catechol, hydroquinones, 2,2-
Base) propane, double (hydroxy phenyl) methane, double (hydroxynaphenyl) methane, tetramethyl biphenyl phenol, xenol, three (hydroxy phenyl) first
Alkane etc..Wherein, preferred phenol.These phenol can be used alone or be used with its any combination of two or more.
For prepare the solid phenolic resin aldehyde species also without any limitation, such as can include it is following in
Any one：Formaldehyde, paraformaldehyde, metaformaldehyde, acetaldehyde, para-acetaldehyde, furfural, benzaldehyde etc..These aldehyde can be independent
Used using or with its any combination of two or more.
The solid phenolic resin that the present invention uses can be powdery or graininess, can be commercially available powdered phenol-formaldehyde resin,
Used after can also commercially available solid phenolic resin be crushed with industrially conventional any disintegrating apparatus.
Foaming of phenolic resin agent in phenol resin composition of the present invention various can be used for phenol to be existing in the prior art
The foaming agent of urea formaldehyde foaming, it is foaming of the blowing temperature less than the heat resisting temperature of expanded resin beads of the present invention
Agent.It is able to can either make in the curing agent of phenolic resin of Foaming of phenolic resin for CBA, physical blowing agent
It is at least one.
Wherein CBA can be the mixture of following material or following material, but be not limited only to following material：It is even
Nitrogen compound, carbonic acid compound and hydrazide-based compound, wherein specifically may include azo dicarbonamide, azodiisobutyronitrile, benzene
Sulfohydrazide, 4,4- oxybenzene sulfonyls base-semicarbazides, p-toluenesulfonyl-semicarbazides, Barium azodicarboxylate, N, N '-dimethyl-N,
N ' dinitroso pentamethylene tetramines and trihydrazinotriazine etc..Wherein physical blowing agent can be at least one of following material,
But it is not limited only to following material：Pentane, fluorohydrocarbon (hydrofluorocarbons, HFC), chlorine fluorohydrocarbon
(hydrochlorofluorocarbons, HCFC) and perfluorinate or partially fluorinated ether.Can wherein phenolic resin be sent out
The curing agent of the phenolic resin of bubble can be the mixture of following material or following material, but be not limited only to following material：Six times
Tetramine, aniline, melamine etc..
Further, it is also possible to phenolic resin cell nucleation in the prior art is added in the solid phenolic resin as needed
Agent, phenolic resin Nucleating Agent can be at least one of following material, but be not limited only to following material：Titanium dioxide
It is silicon, calcium carbonate, talcum powder, zinc oxide, borax, Firebrake ZB, aluminium hydroxide, magnesia, carbon black, benzoic acid, o-2 potassium acid, right
Phthalic acid, benzene sulfonic acid sodium salt, sodium benzoate, y-bend benzyl sorbitol etc., its dosage are usually solid phenolic resin weight
0.01%~5%.
It can be used in the solidification process of phenolic resin or without using curing agent (some phenolic resin such as thermosetting phenolic tree
Fat can directly heat solidification, can be without using curing agent), curing agent can be that can be used for phenolic resin curing in the prior art
Various curing agent, such as various formaldehyde derivatives, hexamethylenetetramine, paraformaldehyde, hexa methoxy melamine, inclined benzene three
Acid anhydrides, epoxy resin, resol, melmac, pre-reaction epoxy-polyester resin and/or other are known solid
Agent etc..The dosage of curing agent is conventional amount used.
The filler commonly used in phenolic resin manufacture field can be also added in above-mentioned composition, such as filler, solidification promote
Agent, foam stabilizer, lubricant, colouring agent, plasticizer, processing aid etc..The filler loading is conventional amount used, or according to reality
The requirement of border situation is adjusted.
Foaming base resin is that heat distortion temperature is higher than 90 under 0.45MPa loads used by the expanded resin beads
DEG C, preferably above 100 DEG C, more preferably higher than 110 DEG C of resin.
The heat distortion temperature of high polymer material as foaming base resin is tested according to GB/T 1634-2004, is surveyed
Load used in examination is 0.45MPa, heating rate (120 ± 10) DEG C/h.
Foaming base resin specifically includes at least one of following various resins used by above-mentioned expanded resin beads：
(1) olefin homo and/or olefin copolymer；(2) poly(4-methyl-1-pentene)；(3) polyamide and/or its modified product；
(4) polycarbonate resin and/or its modified product；(5) homopolymerization and/or copolymerized methanal；(6) different monounsaturated dicarboxylic acids and dihydric alcohol
Pass through linear polyester made from polycondensation reaction；(7) polymerization that aromatic ring macromolecule, i.e. molecule are only made up of aromatic ring and linking group
Thing, such as polyphenyl, polyphenylene oxide, polyphenylene sulfide, polyarylsulfone (PAS), poly aryl ketone, Aromatic polyester, aromatic polyamides；(8) heterocyclic polymer, i.e.,
There are the high polymer material of heterocycle, such as polybenzimidazoles on molecular backbone in addition to aromatic ring；(9) fluoropolymer etc..
Foaming base resin preferably includes at least one of olefin homo and/or olefin copolymer, such as：(1) propylene
Homopolymer and/or propylene copolymer；(2) Alathon and/or ethylene copolymer.
Foaming base resin more preferably includes at least one of Noblen and/or propylene copolymer.
The expansion ratio of above-mentioned expanded resin beads is 0.5~100 times, preferably 1~70 times, more preferably 1~50 times, is entered
Preferably 40~50 times of one step.
The expansion ratio b of expanded resin beads is by by the density p of base resin1Divided by expanded resin beads is apparent
Density p2(b=ρ1/ρ2) obtain.The apparent density ρ of expanded resin beads2It is determined as follows：About 5g expanded resin beads are existed
48 hours are stood at 23 DEG C in air, a graduated cylinder is taken, by expanded resin beads in 23 DEG C of water for being immersed in the graduated cylinder.From
The increment of the volume determines the apparent volume (v) of expanded resin beads.By the quality (m) of expanded resin beads divided by its apparent body
Product can be obtained by apparent density (ρ2=m/v).
Expanded resin beads of the present invention can select the existing Foamex for meeting application claims in the prior art
The commercially available prod of bead, it can also make by oneself.The preparation method of the expanded resin beads of the present invention is existing in the prior art
Expanded resin beads preparation method, without any restrictions, as long as meeting the requirement can of expansion ratio, such as it can use and squeeze
Go out foaming or be prepared by autoclave foam process.
The method of expanded resin beads is wherein prepared using extrusion foaming technique can use such as patent CN1188264C,
CN1861368A, CN101352923B methods described are carried out.Specific method includes one or more base resins are (such as a kind of
Or a variety of polypropylene) and foaming agent it is well mixed after, by extrusion system melting extrusion, ensure extrusion system in extrusion
Temperature and pressure condition is enough to maintain resin and foaming agent to be homogeneous molten condition in extrusion or melt dispersion, then
The extruded machine die extrusion foaming of well mixed resin and foaming agent and pelletizing, are finally made expanded resin beads.
Used foaming agent can be physical blowing agent or CBA.
Physical blowing agent can be injected into base resin in the form of gas, supercritical fluid or liquid.Consider
The toxicity of foaming agent, vapour pressure distribution, the dissolubility of processing difficulty or ease and base resin used, it is preferably non-combustible, nontoxic, do not disappear
Consume foaming agent such as carbon dioxide, nitrogen gas and water, the SF of ozone6, nitrous oxide, argon gas, helium, inert gas such as xenon, air
(nitrogen and oxygen admixture), and the admixture of these materials, flammable foaming agent such as pentane, butane and other can also be selected
Organic material.Other suitable physical blowing agents include, such as fluorohydrocarbon (hydrofluorocarbons, HFC), chlorine fluorohydrocarbon
(hydrochlorofluorocarbons, HCFC) and perfluorinate or partially fluorinated ether.
CBA is added in polymer at a temperature of less than foaming agent decomposition temperature, typically enter extruder it
In preceding addition base resin.When resin is heated to above foaming agent decomposition temperature, CBA activates, and foaming agent decomposes
Discharge gas such as N2、CO2And/or H2O.Foaming agent can be following material but be not limited only to following material：Azo, carbonic ether
And hydrazide-based compound, including it is azo dicarbonamide, azodiisobutyronitrile, benzene sulfonyl hydrazide, 4,4- oxybenzene sulfonyls base-semicarbazides, right
Tosyl-semicarbazides, Barium azodicarboxylate, N, N '-dimethyl-N, N ' dinitroso pentamethylene tetramine and trihydrazinotriazine
Deng.
Foaming agent consumption is adjusted according to the expansion ratio of required expanded resin beads.
Nucleating Agent can also be added as needed during preparing expanded resin beads using extrusion foaming technique,
Nucleating Agent can be following material but be not limited only to following material：Silica, calcium carbonate, talcum powder, zinc oxide, boron
Sand, Firebrake ZB, aluminium hydroxide, magnesia, carbon black, benzoic acid, o-2 potassium acid, terephthalic acid (TPA), benzene sulfonic acid sodium salt, benzoic acid
Sodium, y-bend benzyl sorbitol etc., its dosage are usually the 0.01%~5% of base resin weight.
It can also be added as needed during preparing expanded resin beads using extrusion foaming technique conventional general
Plastic processing additives, such as antioxidant, aid anti-oxidants, lubricant, color masterbatch, dosage are conventional amount used.
It can be single screw extrusion machine, two strings that the extruder used in expanded resin beads is prepared using extrusion foaming technique
Connection formula single screw extrusion machine, parallel dual-screw extruding machine, parallel dual-screw extruding machine series connection single screw extrusion machine, incongruous double screw
One kind in extruder, conical double screw extruder, three-screw extruder.
The method of expanded resin beads is prepared using autoclave foam process to be used such as Publication No. CN1474849A
Method described in Chinese patent is carried out.Such as it can use and base resin is prepared into tree by any applicable known method
Fat particulate, then, the resin particle is set to foam with foaming agent, the resin beads finally to be foamed.Wherein make this with foaming agent
The step of resin particle foams can use common foaming method to carry out, such as in a closed container, be deposited in foaming agent
In case, by the dispersing resin microparticles in decentralized medium, then heating is so that foaming agent is impregnated into resin particle.Will
The pressure and temperature of the closed container is maintained under the pressure condition and temperature conditionss for being enough the resin particle is foamed, Ran Hou
Component in closed container is discharged into a kind of atmosphere of the pressure lower than the pressure in the closed container under the conditions of this, so as to
The resin beads to be foamed.
Above-mentioned decentralized medium can be any decentralized medium, as long as it can make the dispersing resin microparticles in wherein but not
Dissolve the resin particle.The example of the decentralized medium includes water, ethylene glycol, methanol, glycerine, ethanol or its mixture.It is excellent
Select a kind of aqueous dispersion medium.
It is melt bonded between resin particle in foaming process in order to prevent, it can also typically add into decentralized medium
Add a kind of dispersant of the micro-solid of organic or inorganic.It is general to use inorganic powder materials such as natural or synthesis viscous
Native mineral (such as kaolin, mica, clay), alumina, titanium dioxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate and oxidation
Magnesium etc..For the resin particle of every 100 parts by weight, the dosage of dispersant is generally 0.001~5 parts by weight.
It can be any organically physics hair to prepare foaming agent used in expanded resin beads using autoclave foam process
Infusion or any inorganic physical blowing agent or its mixture.Wherein organic physical blowing agents can be following material but not
It is only limited to following material：Propane, butane, pentane, hexane and heptane, alicyclic hydro carbons such as cyclobutane and hexamethylene, and
Halogenated hydrocarbon such as chlorofluoromethane, fluoroform, 1,2- Difluoroethanes, 1,2,2,2- HFC-134as, methyl chloride, ethyl chloride and two
Chloromethanes.Inorganic physical blowing agent can be following material but be not limited only to following material：Air, nitrogen, carbon dioxide, oxygen
Gas, argon gas and water.These organic and inorganic foaming agents can be used alone, and can also make as the mixture of two or more
With.In view of the low cost and environmental problem of Foamex, air or nitrogen are optimal foaming agent.Water as foaming agent can
The water of the decentralized medium of the dispersing resin microparticles to be as making.
The quantity of the foaming agent can be according to the species of the foaming agent, the foaming of blowing temperature, the Foamex to be produced
Multiplying power is suitably adjusted.
Nitrile rubber particle in phenol resin composition of the present invention is the rubber particles with cross-linked structure, its average grain
Footpath is 0.02~1 μm, and preferably 0.05~0.5 μm, more excellent is 0.05~0.2 μm.Its gel content in 60% weight or higher,
It is preferred that 75% weight or higher, more preferably 85% weight or higher.Preferably it is the nitrile rubber particle of equal phase structure.
Above-described nitrile rubber particle is preferably in the international monopoly submitted on the 18th of September in 2000 according to the applicant
The world that application WO01/40356 (priority date on December 3rd, 1999) and the applicant submitted on June 15th, 2001 is specially
Vulcanized Powdered Nitrile Rubber prepared by profit application WO 01/98395 (priority date on June 15th, 2000).This kind of full vulcanization
PNBR refers to gel content up to 60% weight or higher, and more excellent is 75% weight or higher, after drying need not plus every
It is free flowable nitrile rubber micro mist from agent.The average grain diameter of PNBR is 0.02~1 μ in above-mentioned patent application
M, preferably 0.05~0.5 μm, more excellent is 0.05~0.2 μm.Each particulate in above-mentioned Vulcanized Powdered Nitrile Rubber
It is homogeneous, i.e., single particulate is all homogeneous in composition, without discovery point in particulate under the observation of existing microtechnic
The not homogeneous phenomenon such as layer, split-phase.The powdered rubber be by by corresponding rubber latex cross-linking radiation by rubber granule seed
What footpath was fixed.
A kind of expanded material of the present invention, including the phenolic resin as matrix resin for solidifying and foaming and be dispersed therein
The nitrile rubber particle and expanded resin beads, and be prepared by phenol resin composition of the present invention.
The preparation method of expanded material of the present invention includes the either method in following methods：
Method 1 includes：Component including each component comprising the phenol resin composition is well mixed, makes it afterwards
In solid phenolic resin solidify and foam.
Mixing apparatus used in above-mentioned blend step is the conventional mixing apparatus of plastics processing industry, such as high-speed stirred
Machine, planetary mixer, cone-type mixer, V-Mixer, Agravicmixer, double-cone mixer, colter mixer, ribbon mix
Conjunction machine, double helical ribbon mixer, de-airing mixer, high speed dispersor, double-shaft paddle continuous mixer, kneader etc..
Method 2 comprises the following steps：
Step 1) includes：Solid phenolic resin and the Foaming of phenolic resin agent will first be included, nitrile rubber particle exists
After interior component melts blending, crushed after cooling；
Step 2) includes：The blend that step 1) is obtained is well mixed with the component including expanded resin beads again, it
After solidify solid phenolic resin therein and foam.
Melting mixing process can often be carried out in thermosetting resin with mixing apparatus in step 1), such as Single screw extrusion
Machine, double screw extruder, banbury, opening rubber mixing machine etc., what the temperature during melting mixing was commonly used using phenolic resin
Processing temperature, as long as foaming agent, which is not decomposed or expanded, makes Foaming of phenolic resin can.The cooling of mixture in step 1)
There is no particular/special requirement with crushing process, the cooling just commonly used using phenolic resin and disintegrating process and equipment can.
Mixing apparatus used in the blend step of step 2) is the conventional mixing apparatus of plastics processing industry, such as at a high speed
Mixer, planetary mixer, cone-type mixer, V-Mixer, Agravicmixer, double-cone mixer, colter mixer, spiral shell
Band mixer, double helical ribbon mixer, de-airing mixer, high speed dispersor, double-shaft paddle continuous mixer, kneader etc..
Above-mentioned blend step can also add in phenolic resin manufacture field commonly use auxiliary agent, such as filler, curing accelerator,
Lubricant, colouring agent, plasticizer, processing aid etc..The auxiliary dosage is conventional amount used, or the requirement according to actual conditions
It is adjusted.
The addition of above-described various auxiliary agents can be together well mixed in method 1 with all components, in method 2
It can in step 1 add, can also add in step 2.
The expanded material of the present invention is not influenceed by phenolic resin curing system, as long as making the resistance to of the expanded resin beads
Hot temperature is higher than the solidification temperature of solid phenolic resin.Heat resisting temperature herein is that the expanded resin beads collapse bubble
Critical-temperature.
In the solidification process of the solid phenolic resin if using curing agent, curing agent can be various in the prior art
Formaldehyde derivatives, hexamethylenetetramine, paraformaldehyde, hexa methoxy melamine, trimellitic anhydride, epoxy resin, first rank phenol
At least one of urea formaldehyde, melmac, the epoxy-polyester resin of pre-reaction and/or other known curing agent.Solidification
The dosage of agent is conventional amount used.It if using curing agent in method 2, can add in step 1), can also be added in step 2),
If added in step 1), for guarantee phenolic resin curing reaction and the temperature not foamed do not occur for melting temperature.By phenol
The mixing that the equipment of the curing agent of urea formaldehyde composition and phenolic resin mixing can use foregoing plastics processing industry to commonly use is set
It is standby.
The expanded material of the present invention is not influenceed by phenolic resin curing technique, can use phenolic resin in the prior art
Any curing process, such as can use vulcanizing press, tablet press machine, multi-daylight press, baking oven, autoclave, injection
The curing apparatus such as machine.
More than obtained by expanded material due to comprising the crosslinking phenolic resin as matrix resin concurrently steeped and being dispersed therein
Expanded resin beads and with cross-linked structure nitrile rubber particle, make gained expanded material in phenolic resin with certain
Multiplying power foams, and reduces the proportion of expanded material, simultaneously because having the nitrile rubber particle of cross-linked structure in phenolic resin
Presence, make the rate of closed hole of foamed phenolic resin, abscess dispersing uniformity while be improved, because rate of closed hole and abscess disperse
Uniformity improves the final thermal conductivity factor for reducing prepared expanded material.Expanded material obtained by institute's method described above has
More excellent heat-insulating property and outstanding fire resistance.
The moulding material of the present invention, by being made comprising the raw material including phenol resin composition of the present invention, Huo Zheyou
It is made comprising the raw material including expanded material of the present invention, or its manufacture method includes expanded material of the present invention
Preparation method.The moulding material of the present invention, which can be used as, meets the incombustible acoustic material of naked light, vibration-absorptive material, imitated wood material etc.,
It can especially be used as the incombustible insulation material of chance naked light of various highly effective and safes, such as can be as building trade
The heat preservation plate material that naked light is incombustible, safe is met to use.
Embodiment
The present invention is further described with embodiment below, but the scope of the present invention is not restricted by the embodiments.This
The scope of invention is determined by claims.
Embodiment 1
By acrylic resin (Zhenghai refinery, HMS20Z, 110 DEG C of heat distortion temperature under 0.45MPa loads) 100 parts by weight,
The parts by weight of talcum powder 2, which are put into homogenizer, to be sufficiently mixed, and gained mixture is added in single screw extrusion machine through charge door, control
135 DEG C of die temperature processed, pressure 12MPa.By the blowing agent injection port on extruder barrel with 10MPa pressure to
Foaming agent carbon dioxide is injected in polypropylene resin composite melt.Then by circular hole die extrusion of the melt through diameter 2mm, hair
Bubble, pelletizing, cooling, expanded polypropylene beads are obtained after drying, expansion ratio is 45 times.
By powdered phenol-formaldehyde resin (Xinxiang Bai Ma sails Industrial Co., Ltd., 2123), curing agent (hexamethylenetetramine, work
Industry level, Beijing Yili Fine Chemicals Co., Ltd. production), Foaming of phenolic resin agent (ACP-W, great achievement chemical industry section of Beijing Cigna
Skill Co., Ltd, blowing temperature be higher than 110 DEG C) and Vulcanized Powdered Nitrile Rubber (in the extra large latex Co., Ltd that Cixi City is prosperous
NBR-26 emulsion in, by emulsion dry glue weight 3% add crosslinking coagent trimethylolpropane trimethacrylate after, carry out
Radiation vulanization, dose of radiation 2.5Mrad obtain the rubber particles of equal phase structure after spray-dried, its average grain diameter is
100nm, gel content by weight percentage for 85.3%) add homogenizer in be sufficiently mixed after by twin-screw extrusion
Machine obtains mixture, and the wherein weight of curing agent hexamethylenetetramine and powdered phenol-formaldehyde resin ratio is 12/100, form of finely divided powder, mehtod
The weight of nitrile rubber and powdered phenol-formaldehyde resin ratio is 2/100, Foaming of phenolic resin agent (ACP-W) and powdered phenol-formaldehyde resin weight
Than for 5/100.Expanded polypropylene beads are added after cooling crush wherein, are discharged after well mixed, wherein, powdered phenol-formaldehyde resin
Volume ratio with expanded polypropylene beads is 30/70.
Tablet press machine is warming up to 120 DEG C, above material is put into mould and is molded on tablet press machine.In gained print
Foaming of phenolic resin multiplying power is 3 times.The print of gained is subjected to properties test, measures that the results are shown in Table 1.
Thermal conductivity factor is tested according to the standards of GB/T 10297.Impact property is tested according to the standards of GB/T 1843.
Combustibility is then that print is placed on alcohol blast burner to be subjected to after flame sprays 10 minutes, observes the state of print.Foamable phenolic
The rate of closed hole of resin is tested using Kang Ta companies of U.S. production UPYC1200e type real density instrument according to GB/T 10799-2008.
Comparative example 1
Except the weight of Vulcanized Powdered Nitrile Rubber and powdered phenol-formaldehyde resin ratio be 0/100 in addition to, remaining with the phase of embodiment 1
Together, measure that the results are shown in Table 1.
Embodiment 2
Except the weight of Vulcanized Powdered Nitrile Rubber and powdered phenol-formaldehyde resin ratio be 5/100 in addition to, remaining with the phase of embodiment 1
Together, measure that the results are shown in Table 1.
Embodiment 3
Except the weight of Vulcanized Powdered Nitrile Rubber and powdered phenol-formaldehyde resin ratio be 10/100 in addition to, remaining with embodiment 1
It is identical, measure that the results are shown in Table 1.
Embodiment 4
Except the weight of Vulcanized Powdered Nitrile Rubber and powdered phenol-formaldehyde resin ratio be 20/100 in addition to, remaining with embodiment 1
It is identical, measure that the results are shown in Table 1.
From the results shown in Table 1, add after powdered rubber, the rate of closed hole of sample is improved, the heat conduction of sample
Coefficient declines so that the thermal and insulating performance of sample is improved.
Table 1
Claims (27)
1. a kind of phenol resin composition, include the following components of blending：Solid phenolic resin, Foaming of phenolic resin agent, hair
Steep resin beads and nitrile rubber particle, wherein the volume ratio of the solid phenolic resin and expanded resin beads be 5 ︰ 95~
95 ︰ 5；Counted by 100 parts by weight of the solid phenolic resin, described nitrile rubber particle is 0.5~95 part, the phenolic aldehyde
Resin expanded dose is 0.5~50 part；Foaming base resin is hot under 0.45MPa loads used by the expanded resin beads
Deformation temperature is higher than 90 DEG C of resin；The nitrile rubber particle is the nitrile rubber particle with cross-linked structure, its average grain
Footpath is 0.02~1 μm, and gel content is 60% weight or higher.
2. phenol resin composition according to claim 1, the used foaming base resin of the expanded resin beads
For resin of the heat distortion temperature higher than 100 DEG C under 0.45MPa loads.
3. phenol resin composition according to claim 2, the used foaming base resin of the expanded resin beads
For resin of the heat distortion temperature higher than 110 DEG C under 0.45MPa loads.
4. phenol resin composition according to claim 1, it is characterised in that the solid phenolic resin and Foamex
The volume ratio of bead is the ︰ 20 of 5 ︰ 95~80.
5. phenol resin composition according to claim 4, it is characterised in that the solid phenolic resin and Foamex
The volume ratio of bead is the ︰ 60 of 5 ︰ 95~40.
6. phenol resin composition according to claim 1, it is characterised in that using the solid phenolic resin as 100 weight
Number meter, described nitrile rubber particle are 1~45 part.
7. phenol resin composition according to claim 6, it is characterised in that using the solid phenolic resin as 100 weight
Number meter, described nitrile rubber particle are 1~30 part.
8. phenol resin composition according to claim 1, it is characterised in that using the solid phenolic resin as 100 weight
Number meter, the Foaming of phenolic resin agent are 1~30 part.
9. phenol resin composition according to claim 1, it is characterised in that using the solid phenolic resin as 100 weight
Number meter, the Foaming of phenolic resin agent are 1~20 part.
10. phenol resin composition according to claim 1, it is characterised in that sent out used by the expanded resin beads
Steeping base resin includes at least one of following various resins：(1) olefin homo and/or olefin copolymer；(3) polyamide
Resin and/or its modified product；(4) polycarbonate resin and/or its modified product；(5) homopolymerization and/or copolymerized methanal；(6) no
Pass through linear polyester made from polycondensation reaction with monounsaturated dicarboxylic acid and dihydric alcohol；(7) aromatic ring macromolecule；(8) heterocyclic polymer；
(9) fluoropolymer.
11. phenol resin composition according to claim 10, it is characterised in that used by the expanded resin beads
Foaming base resin is poly(4-methyl-1-pentene).
12. the phenol resin composition according to any one of claim 1~10, it is characterised in that the Foamex pearl
Foaming base resin includes at least one of olefin homo and/or olefin copolymer used by grain.
13. the phenol resin composition according to any one of claim 1~10, it is characterised in that the Foamex pearl
Foaming base resin includes at least one of following material used by grain：(1) Noblen and/or propylene copolymer；
(2) Alathon and/or ethylene copolymer.
14. phenol resin composition according to claim 10, it is characterised in that the aromatic ring macromolecule includes polyphenyl, gathered
At least one of phenylate, polyphenylene sulfide, polyarylsulfone (PAS), poly aryl ketone, Aromatic polyester and aromatic polyamides；The heterocyclic polymer bag
Include polybenzimidazoles.
15. phenol resin composition according to claim 1, it is characterised in that the expansion ratio of the expanded resin beads
For 0.5~100 times.
16. phenol resin composition according to claim 15, it is characterised in that the foaming of the expanded resin beads times
Rate is 1~70 times.
17. phenol resin composition according to claim 16, it is characterised in that the foaming of the expanded resin beads times
Rate is 1~50 times.
18. phenol resin composition according to claim 1, it is characterised in that the nitrile rubber particle is equal phase structure
Rubber particles.
19. phenol resin composition according to claim 1, it is characterised in that the average grain diameter of the nitrile rubber particle
For 0.05~0.5 μm.
20. phenol resin composition according to claim 19, it is characterised in that the average grain of the nitrile rubber particle
Footpath is 0.05~0.2 μm.
21. phenol resin composition according to claim 1, it is characterised in that the gel content of the nitrile rubber particle
For 75% weight or higher.
22. a kind of expanded material, it is prepared by the phenol resin composition described in any one of claim 1~21, including
The solid phenolic resin matrix for solidifying and foaming and expanded resin beads and the nitrile rubber grain being dispersed therein
Son.
23. expanded material according to claim 22, it is characterised in that the preparation method of the expanded material includes following
Either method in method：
Method 1 includes：The each component for the phenol resin composition described in any one that the claim 1~21 will be included exists
Interior component is well mixed, and is afterwards solidified solid phenolic resin therein and is foamed；
Method 2 includes：Step 1), it will first include solid phenolic resin and the Foaming of phenolic resin agent, nitrile rubber particle
After component melts blending inside, crushed after cooling；Step 2), the blend for obtaining step 1) again with the Foamex pearl
Component including grain is well mixed, and is afterwards solidified solid phenolic resin therein and is foamed.
24. a kind of preparation method of expanded material according to claim 22 or 23, including either one in following methods
Method：
Method 1 includes：Component including each component that described phenol resin composition will be included is well mixed, and makes it afterwards
In solid phenolic resin solidify and foam；
Method 2 includes：Step 1), it will first include solid phenolic resin and the Foaming of phenolic resin agent, nitrile rubber particle
After component melts blending inside, crushed after cooling；Step 2), the blend for obtaining step 1) again with the Foamex pearl
Component including grain is well mixed, and is afterwards solidified solid phenolic resin therein and is foamed.
25. a kind of moulding material, it is characterised in that as the phenol resin composition described in any one comprising claim 1~21
Raw material inside is made, and is either made up of the raw material including the expanded material described in comprising claim 22 or 23 or it is made
The method of making includes the preparation method of the expanded material described in claim 24.
26. moulding material according to claim 25, it is characterised in that the moulding material is insulation material, sound insulation material
Material, vibration-absorptive material or imitated wood material.
27. moulding material according to claim 26, it is characterised in that the moulding material is heat preservation plate material.
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| CN107459768B (en) * | 2017-08-23 | 2019-12-24 | 广州恒越包装材料有限公司 | Method for foaming and toughening phenolic plastic by using expanded microspheres |
| CN109721916A (en) * | 2019-02-15 | 2019-05-07 | 铜陵市启动电子制造有限责任公司 | A kind of high damping noinductive capacitor padded coaming and preparation method thereof |
| CN111019247B (en) * | 2019-12-19 | 2022-09-13 | 宁波长阳科技股份有限公司 | Foaming material, preparation method thereof and foaming product |
| CA3164701A1 (en) * | 2020-01-16 | 2021-07-22 | Nobuki Hiramatsu | Phenolic resin foam laminate board and composite board |
| CN112225938A (en) * | 2020-09-27 | 2021-01-15 | 惠州市峄董塑胶科技有限公司 | Formula and process for foaming various plastics |
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