CN109705393B - Urea formaldehyde foam material with ultralow water absorption rate and preparation method thereof - Google Patents
Urea formaldehyde foam material with ultralow water absorption rate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a urea formaldehyde foam material with ultra-low water absorption and a preparation method thereof, and is characterized in that: the urea formaldehyde foam material with the ultralow water absorption rate is prepared by adopting a simple and easy-to-implement surface treatment technology, utilizing long-chain alkyl with low surface energy and a siloxane compound to construct a urea formaldehyde surface hydrophobic coating, forming strong interaction such as covalent bonds, and simultaneously adopting inorganic nano particles to form a micro-nano coarse structure on the surface of the urea formaldehyde foam, so that a firm hydrophobic and hydrophobic structure on the surface of the urea formaldehyde foam is constructed, the water absorption rate of the foam is greatly reduced, the urea formaldehyde foam material with the ultralow water absorption rate is endowed with a lasting hydrophobic property.
Description
A technical field
The invention relates to a urea formaldehyde foam material with ultralow water absorption and a preparation method thereof, belonging to the technical field of surface modification of high polymer materials.
Second, background Art
The foam plastic has wide application and huge market, and the commonly used foam plastics such as Polystyrene (PS), polypropylene (PP), Polyurethane (PU) foam and the like have excellent performance, but are easy to burn, and molten drops and highly toxic smoke can be generated in the burning process, so that the potential safety hazard is great. The urea-formaldehyde (UF) foam is amino foam which is obtained by taking resin obtained by condensation polymerization of urea and formaldehyde as a matrix and then foaming and curing, has a unique molecular structure, so that the urea-formaldehyde resin and a foam product thereof have excellent intrinsic flame retardant property, can reach a flame retardant level without adding a flame retardant additive, have remarkable price and fireproof performance advantages compared with foam materials such as PS and PU, and have wide application prospects in the fields of heat insulation, sound absorption and insulation, packaging and shock absorption, dust prevention and explosion suppression, and the like. However, the urea formaldehyde molecular chain segment contains more polar groups such as amino, imino, carbonyl, hydroxymethyl and the like, so that the urea formaldehyde molecular chain segment has poor water resistance and is easy to absorb water, the weight of a product is increased seriously after water absorption, the mechanical property is greatly deteriorated, the heat insulation and sound absorption performance is obviously reduced, and the actual production and application of the urea formaldehyde molecular chain segment are seriously hindered.
Currently, most researches mainly include that modifiers such as melamine, polyvinyl alcohol and cellulose are added into a urea-formaldehyde synthesis system to improve the water resistance of urea-formaldehyde resin, for example, CN201710641554.3 adopts bacterial cellulose loaded with aluminum ions and oxidized corn starch emulsion to modify urea-formaldehyde resin, and a composite network structure formed between the modifier and the urea-formaldehyde resin is utilized to enhance the cross-linking degree of the system, so as to improve the strength and the water resistance of the urea-formaldehyde resin; CN201410611186.4 adopts melamine modified urea formaldehyde foam to prepare melamine urea formaldehyde resin, and the introduction of triazine heterocycle seals a part of hydrophilic groups on the resin, so that the water resistance of the resin is improved; CN201410279922.0 adopts polyvinyl alcohol modified urea-formaldehyde resin to prepare the water-resistant urea-formaldehyde resin adhesive. However, few research reports on reducing the water absorption rate of the urea-formaldehyde resin and improving the hydrophobic property of the urea-formaldehyde resin are reported, such as rochunhua and the like, and 2017, 44(341), 10-11, phenol is introduced into a urea-formaldehyde resin synthesis system, so that the content of hydrophilic hydroxyl (-OH) in the system is reduced, the content of hydrophobic benzene ring is increased, the hydrophobicity of the product is improved, and when the addition amount of the phenol is 3% of the urea content, the water absorption rate of the urea-formaldehyde resin is the lowest and is 6.985%. The addition of the active monomer phenol has great influence on the activity of the synthesis reaction and the foaming curing reaction of the urea-formaldehyde resin and has adverse influence on the final mechanical property and other physical and chemical properties of the product, so that the dosage of the active monomer phenol is not too large, and the effect of reducing the water absorption rate of the resin is not obvious. Meanwhile, as the urea formaldehyde foam has a porous structure, water molecules are easier to diffuse and enter foam pores to damage a foam wall structure, so that the modification research difficulty for reducing the water absorption rate of the urea formaldehyde foam is higher, and no related literature report exists at present.
Third, the invention
The invention aims to provide a urea formaldehyde foam material with ultralow water absorption and a preparation method thereof aiming at the defects of the prior art, and is characterized in that a simple and easy-to-implement surface treatment technology is adopted, long-chain alkyl with low surface energy and siloxane compounds are utilized to construct a urea formaldehyde surface hydrophobic coating to form strong interaction such as covalent bonds, and meanwhile, inorganic nano particles are utilized to form a micro-nano coarse structure on the surface of the urea formaldehyde foam to construct a firm hydrophobic and hydrophobic structure on the surface of the urea formaldehyde foam, so that the water absorption of the foam is greatly reduced, the urea formaldehyde foam material with ultralow water absorption is endowed with lasting hydrophobic performance, and the urea formaldehyde foam material with.
The aim of the invention is achieved by the following technical measures, wherein the raw material fractions are parts by weight except for special specifications.
The starting raw material formula of the urea formaldehyde foam material with ultra-low water absorption comprises the following components:
wherein the functionalized low surface energy compound is one or more of dodecylamine, dodecyldiamine, hexadecyl dimethyl tertiary amine, octadecyl amine, octanediol, dodecanol, hexadecanol, octadecyl alcohol, perfluorooctyl amine, perfluoroheptyl amine, perfluorooctyl ethyl alcohol, 1H, 11H-perfluoro-1-undecanol, 1,2, 2-tetrahydroperfluorododecyl alcohol, double-end amino silicone oil, single-amino silicone oil, double-end hydroxyl silicone oil and single-end hydroxyl silicone oil;
the inorganic nano particles are one or more of nano silicon dioxide, nano titanium dioxide, nano calcium carbonate, nano calcium silicate, nano aluminum oxide and nano zinc oxide;
the coupling agent 1 is one or more of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4, 4' diisocyanate, pentaerythritol tetraglycidyl ether, ethylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1,3, 5-benzene trimethyl acyl chloride, glyoxal, glutaraldehyde and hexanedial;
the coupling agent 2 is one or more of dodecyl trimethoxy silane, octadecyl trichlorosilane, perfluoro decyl trimethoxy silane, perfluoro decyl trichlorosilane and perfluoro dodecyl trimethoxy silane;
the solvent 1 is one or more of ethanol, isopropanol, N dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and chloroform;
the solvent 2 is one or more of ethanol, cyclohexane, normal hexane, acetone, butanone, cyclohexanone and carbon tetrachloride.
Preparation of urea formaldehyde foam material with ultralow water absorption:
dissolving 0.05-20 parts of coupling agent 1 in 80-99.5 parts of solvent 1 to prepare a pretreatment solution with the concentration of 0.05-20%, then placing the urea-formaldehyde foam in the pretreatment solution, soaking at 20-120 ℃ for 0.5-10 h, and taking out to obtain surface functionalized urea-formaldehyde foam; then, 0.05-20 parts of functionalized low-surface-energy compound is dissolved in 80-99.5 parts of solvent 2 to prepare a solution with the concentration of 0.05-20%, and then the urea-formaldehyde foam with the functionalized surface is placed in the solution and soaked for 0.5-10 hours at the temperature of 20-120 ℃ and then taken out to obtain the urea-formaldehyde foam with the hydrophobic coating on the surface;
further adding 0.05-10 parts of inorganic nanoparticles and 0.05-5 parts of coupling agent 2 into 85-99.9 parts of absolute ethyl alcohol, performing ultrasonic dispersion for 0.5-5 hours at 20-70 ℃, then placing the surface hydrophobization urea formaldehyde foam into the mixture, soaking for 0.5-10 hours at 20-70 ℃, taking out, washing and drying to obtain the urea formaldehyde foam material with ultralow water absorption rate.
Fourthly, the invention has the following advantages
The invention is intended for the preparation of a urea-formaldehyde foam having an ultra-low water absorption, having the following characteristics:
a durable hydrophobic coating is constructed on the surface of the urea-formaldehyde foam by adopting a simple and easy-to-implement surface modification technology, the molecular structure and the cellular structure of the urea-formaldehyde foam are not changed, and the characteristics of the foam body such as mechanical property, heat insulation, sound absorption and the like can be well maintained;
urea formaldehyde foam is pretreated by adopting polyfunctional isocyanate/epoxy/acyl chloride/aldehyde compound, and the surface of the foam is functionally modified through the chemical reaction between active functional groups on the molecular chain of the compound and amino and hydroxyl on the surface of the urea formaldehyde foam, so that more active centers are formed on the surface of the foam; then, by utilizing the chemical reaction between active groups on the molecular chain of the low-surface-energy long-chain alkyl/siloxane compound containing the active groups and active centers on the surface of the foam, hydrophobic chain links with low surface energy are introduced to the surface of the urea-formaldehyde foam in a covalent bond mode to form a hydrophobic coating, and the hydrophobic coating is endowed with lasting hydrophobicity and low water absorption;
modifying inorganic nano particles by using a coupling agent with long-chain hydrophobic chain links, soaking the urea formaldehyde foam body in a solution of the coupling agent, wherein the coupling treatment can improve the hydrophobic degree of the inorganic nano particles and promote the uniform dispersion of the nano particles in a solvent, and can enhance the interface interaction between the inorganic nano particles and a urea formaldehyde foam matrix, so that a uniform surface micro-nano coarse structure which is not easy to fall off is formed on the surface of the urea formaldehyde foam, the hydrophobic property of the urea formaldehyde foam is further improved, and the water absorption rate of the urea formaldehyde foam is reduced.
Fifth, detailed description of the invention
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustration, and are not to be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the above disclosure.
Example 1
Dissolving 18.56g of 1, 6-hexamethylene diisocyanate in 600g of tetrahydrofuran to prepare a pretreatment solution with the concentration of 3%, then placing urea-formaldehyde foam in the pretreatment solution, soaking at 40 ℃ for 0.5h, and taking out the urea-formaldehyde foam to obtain surface functionalized urea-formaldehyde foam; then dissolving 28.95g of double-end aminopropyl silicone oil in 550g of acetone to prepare a solution with the concentration of 5%, then placing the urea-formaldehyde foam with the functionalized surface in the solution, soaking the urea-formaldehyde foam for 5 hours at 40 ℃, and taking out the urea-formaldehyde foam to obtain the urea-formaldehyde foam with the hydrophobic coating on the surface;
and further adding 15.54g of nano titanium dioxide and 2.59g of octadecyltrichlorosilane into 500g of ethanol solution, performing ultrasonic dispersion for 3 hours at 30 ℃, then placing the surface-hydrophobized urea-formaldehyde foam into the ethanol solution, soaking the urea-formaldehyde foam for 5 hours at 50 ℃, taking out, washing and drying to obtain the urea-formaldehyde foam material with ultralow water absorption rate.
The water contact angle of the urea-formaldehyde foam before modification is 122 degrees, and the water absorption rate for 24 hours is 4.58 percent; the urea-formaldehyde foam with durable hydrophobic property has a water contact angle of 152 degrees, a water absorption rate of 1.5 percent in 24 hours, and a water contact angle of 148 degrees after being soaked in water for 7 days, so that the urea-formaldehyde foam has better durable hydrophobic property.
Example 2
Dissolving 61.11g of pentaerythritol tetraglycidyl ether in 550g of ethanol to prepare a pretreatment solution with the concentration of 10%, then placing urea-formaldehyde foam in the pretreatment solution, soaking at 70 ℃ for 3h, and taking out to obtain surface functionalized urea-formaldehyde foam; 61.80g of dodecyl diamine is dissolved in 500g of cyclohexane to prepare a solution of a treatment solution with the concentration of 11%, and then the urea-formaldehyde foam with functionalized surface is placed in the solution and is taken out after being soaked for 3 hours at 70 ℃ to obtain the urea-formaldehyde foam with the hydrophobic coating on the surface;
and further adding 29.73g of nano calcium carbonate and 14.86g of perfluorodecyl trimethoxy silane into 550g of ethanol solution, performing ultrasonic dispersion for 2 hours at 50 ℃, then placing the surface hydrophobization urea formaldehyde foam into the solution, soaking the surface hydrophobization urea formaldehyde foam for 5 hours at 70 ℃, taking out, washing and drying the surface hydrophobization urea formaldehyde foam to obtain the urea formaldehyde foam material with ultralow water absorption rate.
The water contact angle of the urea-formaldehyde foam before modification is 122 degrees, and the water absorption rate for 24 hours is 4.58 percent; the urea formaldehyde foam with durable hydrophobic property has a water contact angle of 150 degrees, the water absorption rate of 24h is only 1.6 percent, and the water contact angle can still be kept at 147 degrees after the urea formaldehyde foam is soaked in water for 7 days, so that the urea formaldehyde foam has better durable hydrophobic property.
Example 3
176.47g of 1,3, 5-benzene trimethyl chloride is dissolved in 1000g of chloroform to prepare a pretreatment solution with the concentration of 15%, and then the urea-formaldehyde foam is placed in the pretreatment solution and is taken out after being soaked for 6h at the temperature of 40 ℃ to obtain the surface functionalized urea-formaldehyde foam; 133.13g of octadecylamine is dissolved in 650g of cyclohexanone to prepare a solution of a treatment solution with the concentration of 17%, and then the urea-formaldehyde foam with the functionalized surface is placed in the solution, soaked for 5 hours at 120 ℃ and taken out to obtain the urea-formaldehyde foam with the hydrophobic coating on the surface;
64.71g of nano zinc oxide and 32.35g of perfluorododecyl trimethoxy silane are further added into 550g of ethanol solution, and are ultrasonically dispersed for 2 hours at 70 ℃, then the surface hydrophobization urea formaldehyde foam is placed in the ethanol solution, and is taken out, washed and dried after being soaked for 10 hours at 50 ℃, so that the urea formaldehyde foam material with ultralow water absorption rate is obtained.
The water contact angle of the urea-formaldehyde foam before modification is 122 degrees, and the water absorption rate for 24 hours is 4.58 percent; the urea formaldehyde foam with durable hydrophobic property has a water contact angle of 155 degrees, a water absorption rate of only 0.9 percent in 24 hours, and a water contact angle of more than 150 degrees after being soaked in water for 7 days, so that the urea formaldehyde foam has better durable hydrophobic property.
Claims (1)
1. The urea formaldehyde foam material with ultralow water absorption is characterized in that the material comprises the following raw material formula components by weight:
wherein the functionalized low surface energy compound is one or more of dodecylamine, dodecyldiamine, hexadecyl dimethyl tertiary amine, octadecyl amine, octanediol, dodecanol, hexadecanol, octadecyl alcohol, perfluorooctyl amine, perfluoroheptyl amine, perfluorooctyl ethyl alcohol, 1H, 11H-perfluoro-1-undecanol, 1,2, 2-tetrahydroperfluorododecyl alcohol, double-end amino silicone oil, single-amino silicone oil, double-end hydroxyl silicone oil and single-end hydroxyl silicone oil;
the inorganic nano particles are one or more of nano silicon dioxide, nano titanium dioxide, nano calcium carbonate, nano calcium silicate, nano aluminum oxide and nano zinc oxide;
the coupling agent 1 is one or more of isophorone diisocyanate, 1, 6-hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane-4, 4' diisocyanate, pentaerythritol tetraglycidyl ether, ethylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1,3, 5-benzene trimethyl acyl chloride, glyoxal, glutaraldehyde and hexanedial;
the coupling agent 2 is one or more of dodecyl trimethoxy silane, octadecyl trichlorosilane, perfluoro decyl trimethoxy silane, perfluoro decyl trichlorosilane and perfluoro dodecyl trimethoxy silane;
the solvent 1 is one or more of ethanol, isopropanol, N dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and chloroform;
the solvent 2 is one or more of ethanol, cyclohexane, normal hexane, acetone, butanone, cyclohexanone and carbon tetrachloride;
the preparation method of the urea formaldehyde foam material with ultralow water absorption rate is characterized by comprising the following steps:
dissolving 0.05-20 parts of coupling agent 1 in 80-99.5 parts of solvent 1 to prepare a pretreatment solution with the concentration of 0.05-20%, then placing the urea-formaldehyde foam in the pretreatment solution, soaking at 20-120 ℃ for 0.5-10 h, and taking out to obtain surface functionalized urea-formaldehyde foam; then, 0.05-20 parts of functionalized low-surface-energy compound is dissolved in 80-99.5 parts of solvent 2 to prepare a solution with the concentration of 0.05-20%, and then the urea-formaldehyde foam with the functionalized surface is placed in the solution and soaked for 0.5-10 hours at the temperature of 20-120 ℃ and then taken out to obtain the urea-formaldehyde foam with the hydrophobic coating on the surface;
further adding 0.05-10 parts of inorganic nanoparticles and 0.05-5 parts of coupling agent 2 into 85-99.9 parts of absolute ethyl alcohol, performing ultrasonic dispersion for 0.5-5 hours at 20-70 ℃, then placing the surface hydrophobization urea formaldehyde foam into the mixture, soaking for 0.5-10 hours at 20-70 ℃, taking out, washing and drying to obtain the urea formaldehyde foam material with ultralow water absorption rate.
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| CN102863154A (en) * | 2012-10-18 | 2013-01-09 | 山东轻工业学院 | Method for preparing super-hydrophobicity surfaces |
| WO2014086983A1 (en) * | 2012-12-06 | 2014-06-12 | Mayr-Melnhof Karton Ag | Process for producing a coated packaging material and packaging material having at least one barrier layer for hydrophobic compounds |
| CN105793195A (en) * | 2014-01-31 | 2016-07-20 | 圣诺普科有限公司 | Hydrophobic fine wet silica, method for producing same, and antifoaming agent |
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