CN107892738A - A kind of hydrophobic melamine foam resin dedicated liquid, preparation method and expanding foam solution prepared therefrom - Google Patents

A kind of hydrophobic melamine foam resin dedicated liquid, preparation method and expanding foam solution prepared therefrom Download PDF

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Publication number
CN107892738A
CN107892738A CN201710342791.XA CN201710342791A CN107892738A CN 107892738 A CN107892738 A CN 107892738A CN 201710342791 A CN201710342791 A CN 201710342791A CN 107892738 A CN107892738 A CN 107892738A
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acid
resin dedicated
dedicated liquid
melamine
functional compounds
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CN107892738B (en
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刘绍英
王公应
李子健
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Chengdu Organic Chemicals Co Ltd of CAS
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Chengdu Organic Chemicals Co Ltd of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • 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
    • 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
    • C08J9/143—Halogen containing compounds
    • 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
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/146—Saturated hydrocarbons containing oxygen and halogen atoms, e.g. F3C-O-CH2-CH3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/32—Modified amine-aldehyde condensateS
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The invention discloses a kind of resin dedicated liquid of hydrophobic melamine foam, preparation method and expanding foam solution prepared therefrom.Resin dedicated liquid is obtained by the polymerizable raw material including following component：The parts by weight of melamine 100；The parts by weight of formaldehyde 40~100；Modified monomer and/or functional compounds are more than 0~10 parts by weight；The parts by weight of catalyst 1~3；The parts by weight of water 50~80.The present invention can prepare density in 6~100kg/m3The soft of controllable adjustment, semi-rigid, hard hydrophobic melamine foam, density ＜ 20kg/m3Soft melamine foamed plastic water absorption rate ＜ 10%, contact angle ＞ 120 (°), density ＞ 25kg/m3Semi-rigid and hard melamine foamed plastic water absorption rate ＜ 5%, contact angle ＞ 130 (°), tensile strength ＞ 120kpa.

Description

A kind of resin dedicated liquid of hydrophobic melamine foam, preparation method and prepared therefrom Expanding foam solution
Technical field
The present invention relates to melamine foam field, further say, be to be related to a kind of hydrophobic melamine foam Resin dedicated liquid, preparation method and expanding foam solution prepared therefrom.
Background technology
Melamine foamed plastic is a kind of foamed material of the natural high fire-retardance with Intrinsical, because it has excellent suction Sound, noise reduction, heat-insulated, high temperature resistant, low smoke rate, easily chemical resistance, the performance such as aft-loaded airfoil, it is set to be filled in building The increasing field such as decorations, public place, electromechanical equipment, vehicular traffic is widely used.
At present, conventional foamed material (such as polyurethane, polystyrene) is in addition to poor flame retardant properties itself, in a fire Produce substantial amounts of cigarette, toxic gas.Show according to statistics, more than 80% fire fatality is all related to poisonous smoke.Trimerization Cyanamide foam can in the case where not adding any fire retardant reach DIN4102 (DIN) defined B1 levels it is low can Combustion property material standard and UL94-V0 (AIA's standard) level high fire-retardance material standard.
The performance of melamine foam is mainly prepared by resin dedicated preparation technology, foaming liquid preparing process, foam (foaming, solidify afterwards etc.) technique and its corresponding special equipment etc. together decides on.
US400050、US4334971、DE870027、FR1073642、CN200810042685.0、US5436278、 The publications such as US6608118, CN200910263526.8, CN201110082559.X are concentrated mainly on melamino-formaldehyde bubble The resins synthesis of foam, foaming formulation aspect.CN200510038093.8、US6608118、CN200910037911.0、 The patents such as CN200880008281.8, CN200680021117.1, CN200910216553.X disclose some processes. US4666948A、EP0017671B1、DE870027、CN103097442A、CN104029326A、CN104031284A、 CN201210010627.6、CN200810049126.2、CN200910263526.8、CN200780011962.5、 The patents such as CN201210529428.6 essentially disclose 4~12kg/m of density3The preparation method of soft melamine foamed plastic. CN104029326A discloses a kind of melamine foamed plastic preparation technology, CN104031284A discloses a kind of melamine foamed plastic The preparation technology of expanding foam solution.CN201210130457.5、CN201210540436.0、CN201210328428.X、 The patents such as CN103146016 disclose the preparation method of hard melamine foamed plastic sheet material.CN CN20141021356 are disclosed A kind of preparation method of melamine foamed plastic expanding foam solution, CN201410213568 disclose a kind of melamine foamed plastic and prepare work Skill.
Melamine foam of the prior art particularly flex foam is perforate, and water absorption rate is very high, leads Cause its application in fields such as building, the vehicles (such as seat of automobile, aircraft, part etc.) exist wretched insufficiency even by To limitation.
CN105295086A discloses maceration extract, preparation method and the impregnation method of soft melamine foamed plastic, with Fluorocarbon resin is maceration extract, soft melamine foamed plastic is placed in maceration extract after dipping extruded, dried successively again, Bake and bank up with earth and cooling treatment, obtain the melamine foamed plastic with hydrophobicity.CN104961908A discloses a kind of hydrophobicity trimerization Cyanamide foam and preparation method thereof, by the way that hydrophober calcium stearate is added after reaction solution mixed foaming and foaming again to foam The dual hydrophobic processing of sprinkling dipping calcium stearate solution is carried out, obtains hydrophobicity melamine foamed plastic.CN105504336A is public A kind of preparation method of hydrophobic type melamine foamed plastic has been opened, hydrophobic is prepared with dimethicone, silane coupler, deionized water Solvent, hydrophobic solvent is uniformly sprayed on melamine foamed plastic semi-finished product by shower nozzle, 5~15min is dried under microwave condition, And moisture vapor is discharged with air blower, obtain hydrophobic type melamine foamed plastic body.These patents are using dipping or spraying waterproof Agent, then through extruding, drying, baking and banking up with earth mode with the after-treatment such as cooling treatment, water resistant layer is formed in foam surface, so as to obtain The melamine foamed plastic of surface hydrophobic.
There is document to disclose and modified cyanurotriamide resin is prepared using modifying agent, such as jade pendant knows brightness with α, ω dihydroxy diformazans Radical siloxane and polyvinyl alcohol are that modifying agent prepares modified melamine-formaldehyde resin, this method can improve resin toughness, Improve the elongation at break of glued membrane, improve the mechanical property and toughness of fiber, but there are some researches show prepared by this kind of method of modifying Melmac can be used for prepare melamine foamed plastic.
What vigorously have studied " melamine resin modification and its foaming technique " for Qingdao University of Science and Technology, have studied modifying agent Influence (including foam unit weight, tensile strength, bending strength, water imbibition etc.) to hard melamine foamed plastic performance.This side Method can prepare 22~50g.cm of unit weight-3Rigid foam, but in the unit weight scope only have 35~40g.cm of unit weight-3Hard bubble Foam the maximum tensile strength is 0.063Mpa, water absorption rate 6%, and other hard foam performances are poor；Unit weight ＜ 20g.cm can not be prepared-3 Flexible foam and unit weight ＞ 50g.cm-3Rigid foam.It can be seen that it is not with hydrophobicity or the preparation of functional monomer Modified cyanurotriamide resin is used equally for preparing melamine foamed plastic and foam has hydrophobicity and preferable mechanical property.
Although above-mentioned patent or public technology propose the method for preparing hydrophobic melamine foam, but it is soft to prepare hydrophobic Melamine is the method for dipping or spraying, and these method complex process, production cost are high, product only surface hydrophobic, product Quality is unstable and only surface tool layer hydrophobic, product after once the damaged or time is longer its hydrophobicity performance decline it is even complete Disappear；Melamine rigid foam can be prepared by modified melamine-formaldehyde resin, but can only prepare unit weight 22~ 50g.cm-3Rigid foam and the unit weight scope in only 35~40g.cm of unit weight-3Rigid foam the maximum tensile strength be 0.063Mpa, water absorption rate 6%, other hard foam performances are poor, it is impossible to meet building, the vehicles (such as automobile, aircraft etc. Seat, part etc.) etc. field requirement.
The content of the invention
The purpose of the present invention is exactly to solve the above problems, there is provided one kind uses modified monomer and/or functional compound Ratio in resin liquid of thing or fabricated in situ functional compounds, regulation and control modified monomer and/or functional compounds, a step process Prepare the resin dedicated liquid of hydrophobic melamine foam and expanding foam solution, directly prepare uniformly, permanently hydrophobic, foam density 8~ 100kg/m3Good soft and hard melamine foamed plastic the methods of mechanical property such as any adjustable, tensile strength.
The present invention can require according to application field, prepare density in 6~100kg/m3The soft of controllable adjustment, semi-rigid, Hard hydrophobic melamine foam, density ＜ 20kg/m3Soft melamine foamed plastic water absorption rate ＜ 10%, contact angle ＞ 120 (°), density ＞ 25kg/m3Semi-rigid and hard melamine foamed plastic water absorption rate ＜ 5%, contact angle ＞ 130 (°), resist Tensile strength ＞ 120kpa.
An object of the present invention is to provide a kind of resin dedicated liquid of hydrophobic melamine foam.
The resin dedicated liquid is obtained by the polymerizable raw material including following component：
The modified monomer is poly glycol monomethyl ether (preferred molecular weight 3000~5000), to the phosphorus of carboxyphenoxy ring three At least one of nitrile, glycine methyl ester, chloro substituted polyphosphazene；
The functional compounds are at least one of functional compounds A, or at least one of functional compounds A and work( One or more of combinations in energy compound B；
The functional compounds A is phosphorus nitrile compounds, APP class compound, organosilicon polymer, fluororesin；
The functional compounds B is to contain aminal, hemiacetal amine, amide groups, amido, hydroxyl, carbonyl, carboxyl or epoxy The compound of group；
The catalyst is diethanol amine, triethanolamine, sodium hydroxide, potassium hydroxide, Boratex, potassium borate, weighting Asia One or more in sodium sulphate, sodium hydrogensulfite.
Wherein, preferably：
The phosphorus nitrile compounds are poly-alkoxyl phosphonitrile, poly- aryloxy group phosphonitrile, poly- fluoroalkyl phosphonitrile or poly- bromo Alkoxy phosphonitrile；
The APP class compound is poly- hydroxy phenyl ammonium phosphate, APP or surface ammonium polyphosphate modifying；
The organosilicon polymer is hydroxyl, containing amino or double bond containing poly-organosilicon alkane or siloxanes.
Compound (i.e. modified monomer and functional compounds) with water resistant group is passed through copolymerization by the invention Mode be connected in the strand of resin dedicated liquid, the foam prepared with the resin dedicated liquid just has uniformly lasting hydrophobic Property.
The second object of the present invention is to provide a kind of preparation method of the described resin dedicated liquid of hydrophobic melamine foam.
Including one of following three kinds of methods：
A) resin dedicated liquid is synthesized using modified monomer：By the modified monomer by the dosage in reaction temperature 60~70 DEG C 30~50min of reaction, then adds described other raw materials, reacts 50~80min at 70~100 DEG C, be made resin dedicated Liquid；
B) resin dedicated liquid is prepared using functional compounds：The use will be pressed except other raw materials of functional compound beyond the region of objective existence Amount adds functional compounds and continues 30~50min of reaction, be made resin dedicated at 70~100 DEG C, 30~40min of reaction time Liquid；
C) resin dedicated liquid is prepared using modified monomer and functional compounds：By the modified monomer by the dosage anti- 60~70 DEG C of 30~50min of reaction of temperature are answered, other raw materials except functional compound beyond the region of objective existence are then added, in 70~100 DEG C of reactions 20~30min, add functional compounds and continue 30~50min of reaction at 70~100 DEG C, resin dedicated liquid is made.
Wherein, preferably：
In method a), described other raw materials are then added, 50~80min is reacted at 85~100 DEG C, is made resin dedicated Liquid；
In method b), reaction temperature is 85~100 DEG C；
In method c), add functional compounds and continue 30~50min of reaction at 85~100 DEG C, resin dedicated liquid is made.
The third object of the present invention is to provide a kind of melamine expanding foam solution.
The melamine expanding foam solution includes：
The surfactant is anion surfactant, cationic surfactant, nonionic surfactant, anti- Answer one or more kinds of compoundings in type surfactant；
The foaming agent is：Water, pentane, hexane, alkoxy fluothane hydrocarbon, petroleum ether, oxalate, CO2Middle a kind of or combination；
The crosslinking agent is：Hydrochloric acid, sulfuric acid, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, boric acid, citric acid, formic acid, acetic acid, oxalic acid, Acrylic acid, p-methyl benzenesulfonic acid, oleic acid, stearic acid, palmitic acid, lactic acid, sulfosalicylic acid, naphthalenedisulfonic acid, maleic acid, polyhydroxy Base acid and one kind in corresponding acid anhydrides or combination；
Described functional compounds A is one kind in phosphorus nitrile compounds, APP, organosilicon polymer, fluororesin It is or a variety of.
Special equipment prepared by the expanding foam solution is combined by delivery pump, mono-/bis-screw extruder or double screw extruder list The compositions such as only use, measuring pump, super mixer；Resin dedicated, surfactant, foam stabilizer, foaming agent, crosslinking agent, auxiliary agent Deng through conveying be pumped into mono-/bis-screw extruder mixing after, then after super mixer mixes obtain high uniformity expanding foam solution.
Melamine foam density prepared by the expanding foam solution of the present invention is in 6~100kg/m3Controllable adjustment, hydrophobicity Uniformly, tensile strength ＞ 120kpa, density ＜ 20kg/m3Soft melamine foamed plastic water absorption rate ＜ 10%, contact angle ＞ 120 (°), density ＞ 25kg/m3Semi-rigid and the water absorption rate ＜ 5% of hard melamine foamed plastic, contact angle ＞ 130 (°) Microwave continuous foam process.
The present invention preferably uses microwave continuous foam process, and the expanding foam solution of preparation is foamed：
Microwave system is made up of the identical or different microwave source of array power, and microwave frequency is 915MHZ or 2450MHZ.It is micro- Ripple field strength distribution is controllable, and the power of microwave source single can both adjust the regulation of and can group, foaming in 10~100% stepless modulations During according to being actually needed, completed jointly using one group or several groups of microwave tube groups.
Using technical scheme can continuous production hydrophobicity uniformly, it is permanent, density is in 6~100kg/m3Controllable tune Section, 120 ° of water absorption rate ＜ 10%, contact angle ＞ hydrophobic melamine foam.
Present invention process is ripe, simple to operate, properties of product are stable, production cost is low, can meet different application leads The requirement in domain, is easy to industrialized production, has filled up the blank of prior art.
Embodiment
With reference to embodiment, the invention will be further described.But it is to technical solution of the present invention that following examples, which are not, Limitation.As long as the technical scheme that can be realized without creative work on the basis of above-described embodiment, is accordingly to be regarded as In the protection domain for entering patent of the present invention.
Embodiment 1
It is prepared by resin dedicated liquid
Raw material proportioning：
By poly glycol monomethyl ether, six pairs of phosphonitriles of carboxyphenoxy ring three, glycine methyl ester add reactor, 60~70 DEG C React 40min；Then other raw materials are added, then 50~80min is reacted at 980 DEG C, resin dedicated liquid is made.
Embodiment 2
It is prepared by resin dedicated liquid
Raw material proportioning：
Melamine, formaldehyde, sodium hydroxide, water are reacted into 40min at 98 DEG C, add poly- aryloxy group phosphonitrile, APP Continue to react 40min, resin dedicated liquid is made.
Embodiment 3
It is prepared by resin dedicated liquid
Raw material proportioning：
By above-mentioned raw materials in 98 DEG C of reaction time 100min, obtained resin dedicated liquid.
Embodiment 4
It is prepared by resin dedicated liquid
Raw material proportioning：
By above-mentioned raw materials in 98 DEG C of 100~120min of reaction time, obtained resin dedicated liquid.
Embodiment 5
The resin liquid prepared with embodiment 1~4 prepares expanding foam solution
Raw material proportioning
Comparative example 1
It is prepared by resin dedicated liquid
Raw material proportioning
By above-mentioned raw materials in 98 DEG C of 100~120min of reaction time, obtained resin dedicated liquid.
It is prepared by expanding foam solution
Comparative example 2
It is prepared by expanding foam solution
Raw material proportioning
Comparative example 3
It is prepared by expanding foam solution
The expanding foam solution that will be prepared respectively in embodiment, according to before inventor patent of invention (ZL2014102135681, Application number 201610456950.4, application number 201610453756.0,2014102135677) prepare the foams of different densities.Bubble The tensile strength of foam is between 120~160kpa, elongation at break ＞ 15%, the foam density of different embodiments preparations, water suction Rate, angle of wetting are as shown in table 1.
Foaming properties prepared by 1 different embodiments of table and comparative example
"-" represents that foam hydrophilic (water suction) or hydrophobicity are very poor, can not measure contact angle.
Sequence number 1~5 represents resin dedicated liquid prepared by embodiment 1 in table 1, after preparing expanding foam solution according to embodiment 6, prepares Melamine foamed plastic performance.
Sequence number 6~10 represents resin dedicated liquid prepared by embodiment 2, after preparing expanding foam solution according to embodiment 5, the three of preparation The performance of poly cyanamid foam.
Sequence number 11~13 represents resin dedicated liquid prepared by embodiment 3 in table 1, after preparing expanding foam solution according to embodiment 5, system The performance of standby melamine foamed plastic.
Sequence number 14~17 represents resin dedicated liquid prepared by embodiment 4 in table 1, after preparing expanding foam solution according to embodiment 5, system The performance of standby melamine foamed plastic.
Sequence number 18~19 represents the performance of melamine foamed plastic prepared by comparative example 1 in table 1.
Sequence number 20~22 represents the performance of melamine foamed plastic prepared by comparative example 2 in table 1.
Sequence number 23~25 represents the performance of melamine foamed plastic prepared by comparative example 3 in table 1.
Table 1 shows：The foam density of the present invention is less than 10Kg/m3To 90Kg/m3All there is preferable hydrophobicity.It is and right Same amount of functional compounds are added in foam prepared by ratio 2 and comparative example 3, although the contrast with being not added with functional compounds Example 1 is compared, and water absorption rate declines many during similar density, but only reaches 35Kg/m in density3When just there is hydrophobicity.

Claims (7)

1. a kind of resin dedicated liquid of hydrophobic melamine foam, it is characterised in that the resin dedicated liquid is by including following component Polymerizable raw material and obtain：
The modified monomer is poly glycol monomethyl ether, to the phosphonitrile of carboxyphenoxy ring three, glycine methyl ester, in chloro substituted polyphosphazene At least one；
The functional compounds are at least one of functional compounds A, or at least one of functional compounds A and functionalization One or more of combinations in compound B；
The functional compounds A is phosphorus nitrile compounds, APP class compound, organosilicon polymer, fluororesin；
The functional compounds B is to contain aminal, hemiacetal amine, amide groups, amido, hydroxyl, carbonyl, carboxyl or epoxide group Compound；
The catalyst is diethanol amine, triethanolamine, sodium hydroxide, potassium hydroxide, Boratex, potassium borate, weighting sulfurous acid One or more in sodium, sodium hydrogensulfite.
2. the resin dedicated liquid of hydrophobic melamine foam as claimed in claim 1, it is characterised in that：
3. the resin dedicated liquid of hydrophobic melamine foam as claimed in claim 1, it is characterised in that：
The phosphorus nitrile compounds are poly- hydroxy phenyl ammonium phosphate, poly-alkoxyl phosphonitrile, poly- aryloxy group phosphonitrile, poly- fluoroalkyl Phosphonitrile or poly- bromo alkoxy phosphonitrile；
The APP class compound is poly- hydroxy phenyl ammonium phosphate, APP or surface ammonium polyphosphate modifying；
The organosilicon polymer is hydroxyl, containing amino or double bond containing poly-organosilicon alkane or siloxanes.
4. a kind of preparation method of resin dedicated liquid of hydrophobic melamine foam as described in one of claims 1 to 3, its feature It is that methods described includes one of following three kinds of methods：
A) resin dedicated liquid is synthesized using modified monomer：The modified monomer is anti-in 60~70 DEG C of reaction temperature by the dosage 30~50min is answered, then adds described other raw materials, 50~80min is reacted at 70~100 DEG C, resin dedicated liquid is made；
B) resin dedicated liquid is prepared using functional compounds：Other raw materials except functional compound beyond the region of objective existence are existed by the dosage 70~100 DEG C of 30~40min of reaction time, add functional compounds and continue 30~50min of reaction, resin dedicated liquid is made；
C) resin dedicated liquid is prepared using modified monomer and functional compounds：By the modified monomer by the dosage in reaction temperature Degree 60~70 DEG C reaction 30~50min, then add except functional compound beyond the region of objective existence other raw materials, 70~100 DEG C react 20~ 30min, add functional compounds and continue 30~50min of reaction at 70~100 DEG C, resin dedicated liquid is made.
5. the preparation method of resin dedicated liquid as claimed in claim 4, it is characterised in that：
In method a), described other raw materials are then added, 50~80min is reacted at 85~100 DEG C, it is resin dedicated that viscosity is made Liquid；
In method b), reaction temperature is 85~100 DEG C；
In method c), add functional compounds and continue 30~50min of reaction at 85~100 DEG C, resin dedicated liquid is made.
6. a kind of melamine expanding foam solution for including the resin dedicated liquid as described in one of claims 1 to 3, it is characterised in that described Melamine expanding foam solution includes：
The surfactant is anion surfactant, cationic surfactant, nonionic surfactant, response type One or more kinds of compoundings in surfactant；
The foaming agent is：Water, pentane, hexane, alkoxy fluothane hydrocarbon, petroleum ether, oxalate, CO2Middle a kind of or combination；
The crosslinking agent is：Hydrochloric acid, sulfuric acid, phosphoric acid, metaphosphoric acid, pyrophosphoric acid, boric acid, citric acid, formic acid, acetic acid, oxalic acid, propylene Acid, p-methyl benzenesulfonic acid, oleic acid, stearic acid, palmitic acid, lactic acid, sulfosalicylic acid, naphthalenedisulfonic acid, maleic acid, polyhydroxy-acid And one kind in corresponding acid anhydrides or combination；
Described functional compounds A is one in phosphazene compound, APP class compound, organosilicon polymer, fluororesin Kind or combination.
7. melamine expanding foam solution as claimed in claim 6, it is characterised in that：
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CN109438642A (en) * 2018-11-19 2019-03-08 中国科学院成都有机化学有限公司 A kind of combustibility A grades melamine foamed plastic and preparation method thereof
CN109749122A (en) * 2019-01-23 2019-05-14 中国石油大学(华东) A kind of hydrophobic ring cross-linking type polyphosphazene composite sponge and its preparation method and application
CN111285987A (en) * 2020-03-27 2020-06-16 浙江亚迪纳新材料科技股份有限公司 Semi-rigid melamine foam plastic and preparation method thereof
CN112063003A (en) * 2019-06-11 2020-12-11 巴斯夫欧洲公司 Method for preparing melamine-formaldehyde foam by using fluorinated foaming agent

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CN103665755A (en) * 2013-11-28 2014-03-26 南通紫鑫实业有限公司 Preparation methods of melamino-formaldehyde resin for foam and melamino-formaldehyde resin foam
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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN109438642A (en) * 2018-11-19 2019-03-08 中国科学院成都有机化学有限公司 A kind of combustibility A grades melamine foamed plastic and preparation method thereof
CN109749122A (en) * 2019-01-23 2019-05-14 中国石油大学(华东) A kind of hydrophobic ring cross-linking type polyphosphazene composite sponge and its preparation method and application
CN109749122B (en) * 2019-01-23 2021-10-08 中国石油大学(华东) Hydrophobic ring cross-linked polyphosphazene composite sponge and preparation method and application thereof
CN112063003A (en) * 2019-06-11 2020-12-11 巴斯夫欧洲公司 Method for preparing melamine-formaldehyde foam by using fluorinated foaming agent
CN111285987A (en) * 2020-03-27 2020-06-16 浙江亚迪纳新材料科技股份有限公司 Semi-rigid melamine foam plastic and preparation method thereof
WO2021189674A1 (en) * 2020-03-27 2021-09-30 浙江亚迪纳新材料科技股份有限公司 Semi-rigid melamine foamed plastic and preparation method therefor
CN111285987B (en) * 2020-03-27 2022-01-18 浙江亚迪纳新材料科技股份有限公司 Semi-rigid melamine foam plastic and preparation method thereof

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