CN102120810A - Preparation method of high solid content expandable melamine modified urea resin - Google Patents
Preparation method of high solid content expandable melamine modified urea resin Download PDFInfo
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Abstract
The invention discloses a preparation method of high solid content expandable melamine modified urea resin. The preparation method is as follows: a non-dehydration preparation process is adopted, paraformaldehyde is depolymerized under the alkaline condition to obtain high concentration formaldehyde solution, and the high concentration formaldehyde solution reacts with urea and melamine to directly prepare the high solid content expandable melamine modified urea resin. The solid content of the prepared urea resin is 70%-80%, the viscosity is 800-1200MPa and the content of free formaldehyde is 0.1%-0.25%. The apparent density of the melamine modified urea resin foam material obtained through foaming is up to 0.03-0.05g/cm<3>, the oxygen index is 50%-70%, the foam material can meet the requirements of the new building material with light weight and fire resistance; and the invention provides a new way for the development and utilization of the fire resistant and environmentally friendly urea resin foam heat insulating material.
Description
Technical field
The present invention relates to a kind of preparation method who is used to prepare the expandable resin of flame retardant type foam materials, relate in particular to a kind of high preparation method who contains the expandability cyanurotriamide modified urea resin admittedly.
Background technology
Urea-formaldehyde foamed plastics is to be made by urea-formaldehyde resin.Germany just developed urea-formaldehyde foamed plastics in 1933, and went into operation in BASF AG in 1940, and states such as American and Britain also successively go into operation.The urea-formaldehyde resin foam is to add behind tensio-active agent, stiffening agent and the stablizer porous foam shape solid that bubbles and form by mechanical stirring or chemistry in urea-formaldehyde resin.Urea formaldehyde condensate foam is cheap and percentage of open area is higher, water-absorbent is better because of its raw materials cost, be widely used in industries such as flower culture and planting lawns, but also there are some shortcomings in it,, poor fire big as not water-fast, the easy age embrittlement of foam and produce and use in exist serious formaldehyde pollution problem.Terpolycyantoamino-formaldehyde resin can be 150 ℃ of uses, and have self-extinguishing, arc resistance and good mechanical performance.Terpolycyantoamino-formaldehyde resin foam materials good flame resistance, percentage of open area is higher, foamy body is high, burst size of methanal is low, be widely used in building sound insulation fields such as music hall, but cost is higher, has limited its widespread use.Therefore, at above-mentioned shortcoming, with a certain amount of trimeric cyanamide urea-formaldehyde resin is carried out modification by copolymerization, the urea-formaldehyde resin after the modification had both had the advantage of terpolycyantoamino-formaldehyde resin concurrently, had remedied the shortcoming of self again.In the urea-formaldehyde resin molecule, introduce trimeric cyanamide, owing to formed tridimensional network, can seal many water-absorbent groups, simultaneously trimeric cyanamide show alkalescence can in and the acid in the resin, prevent and reduced the degraded and the hydrolysis rate of resin to a certain extent, thereby improve the water tolerance of urea-formaldehyde resin.Simultaneously, add flame retardant resistance and the thermostability that trimeric cyanamide can improve urea-formaldehyde resin greatly.On the other hand, the trimeric cyanamide of adding can react with formaldehyde, generates melamine methylol, makes that the free formaldehyde content in the urea-formaldehyde resin descends.
Because urea formaldehyde condensate foam is to generate urea-formaldehyde resin by urea and formaldehyde through polycondensation, then through foaming handle, dryness finalization forms, so this material has that quality is light, the water-absorbent good water-retaining property, make abundant raw material, cheap, advantage such as manufacturing process is simple.Research aspect urea formaldehyde condensate foam at present is more, and applied for a collection of patent of invention: CN 101134803A has proposed a kind of urea-formaldehyde foam plant cultivation substrate and preparation method thereof.The urea-formaldehyde foam plant cultivation substrate that utilizes this technical scheme to obtain has penetrating many foam structures, and good water absorption can satisfy the needs that plant normal growth is grown fully.Compare with existing cultivation apparatus without soil and urea-formaldehyde foam cultivation matrix, the agronomic culture proterties is equal to or is higher than existing cultivation apparatus without soil or matrix.CN 101220172A has proposed a kind of urea formaldehyde condensate foam for thermal insulation of building and manufacture method thereof.This kind foam materials is by adding properties-correcting agent urea-formaldehyde resin prescription, production of resins technology to be optimized a kind of urea aldehyde polycondensate with linear chain structure and part branched structure of acquisition, the foamed solidification agent is that employing sodium butylnaphthalenesulfonate and phosphoric acid are main raw material, foam mixes by pump and spray gun, foaming at the construction field (site), can be full of any irregular space, have good heat insulation, insulation, sound insulation and fire resistance, fire-retardant, nontoxic, smokeless, convenient, durable, the Maintenance free of construction.CN 1736936A and CN 101289567A have proposed two kinds of urea-formaldehyde foam plastic heat-insulating boards and preparation method thereof respectively.Meanwhile, also having a lot of urea-formaldehyde resin foamy United States Patent (USP)s to be seen in reports for work.US3963650 has proposed a kind of with the urea-formaldehyde resin (best 75% or more) of solid content more than 40%, the preparation method of foaming preparation low density self-supporting type urea formaldehyde condensate foam.US3979341 has proposed to make tensio-active agent with dibutyl two naphthene sulfonic acid, phosphoric acid is made solidifying agent, and Resorcinol is done bubble and smeared setting agent, does flame-proof modifier with muriate, isocyanic ester is done plasticized modifier, prepares the method for the urea formaldehyde condensate foam with certain toughness and flame retardant properties.US4069175 has proposed to add acid surface active agent and has promoted the expandability urea-formaldehyde resin to solidify fully in urea-formaldehyde resin stirring foaming process, the method for preparation size stability urea formaldehyde condensate foam.US4092277 has proposed to prepare with the aromatics part instead of formaldehyde of formaldehyde and urea reaction the method for the higher urea formaldehyde condensate foam of chemical stability.US4225680 has proposed to add the alkyl diphenyl ether sodium sulfonate and has made tensio-active agent in the expandability urea-formaldehyde resin of solid content 35%～45%, phosphoric acid is made solidifying agent, lime carbonate is done the abscess-size leveler, polyoxyethylene glycol is done the foam carburization agent, Dyhard RU 100 is done the hydrophobically modified agent, Sodium Bromide is done the aging agent of foam, through stirring the urea formaldehyde condensate foam that foaming obtains having anti-contracility.US4537913 has proposed a kind ofly by add the urea formaldehyde performed polymer in the expandability urea-formaldehyde resin it to be carried out modification, the method for the urea formaldehyde condensate foam of the low formaldehyde remnants of preparation.
Because the melamino-formaldehyde foam is a kind of novel foamed plastic with high opening rate, three-dimensional net structure, so this material has excellent sound absorbing capabilities, flame retardant properties, heat-proof quality, moisture-proof thermostability, safety and sanitation and suitability for secondary processing.Research is also more aspect the terpolycyantoamino-formaldehyde resin foam materials at present, applied for a collection of patent of invention: CN 101671472A has proposed a kind of resin solution and method for making thereof that is used to prepare melamine formaldehyde resin foam plastics, preparation method's following steps of described terpolycyantoamino-formaldehyde resin solution: weak acid strong alkali salt is added resin solution, mix, obtain described terpolycyantoamino-formaldehyde resin solution, described resin solution is the reaction product of trimeric cyanamide and formaldehyde.Experimental results show that the terpolycyantoamino-formaldehyde resin flex foam that adopts terpolycyantoamino-formaldehyde resin formulations prepared from solutions of the present invention, have good mechanical property, physicochemical property and flame retardant properties.CN 1831023A has proposed a kind of production technique of melamine foamed plastic, it is by trimeric cyanamide and formaldehyde production of melamine formaldehyde resin, then through adding whipping agent and acids promotor, in microwave oven, through certain temperature and time, by the microwave heating foaming, and then carry out the high-temperature post-treatment typing, last moulding product.The product that this invention is produced has good security.Reliability and practicality.CN 101415757A has proposed a kind of based on the carbamide condensation product and by the open celled foam of the compound with C6-C20 alkyl (particularly octadecyl) such as aluminum stearate or octadecylisocyanate hydrophobically modified, Preparation Method And The Use.CN 101423648A has proposed a kind of melamine foam material for pipeline heat insulation, and it is made up of the expanding foam solution system, and this expanding foam solution system comprises high body part melamine resin, whipping agent, solidifying agent and emulsifying agent.Thermal conductivity of the present invention is low, soft moderate, easy machine-shaping, construction are simple and solid and reliable.CN 101735555A has proposed a kind of high-flexibility melamino-formaldehyde foam material and preparation method thereof, its preparation is to be mixed with the aqueous solution of determining weight concentration earlier through polyhydroxy compound modified melamino-formaldehyde performed polymer, adding tensio-active agent, whipping agent, promotor, solidifying agent fully mix and are prepared into expanding foam solution, expanding foam solution is put into microwave chemical reactor or high temperature oven, at the 100-300 ℃ of 30s-15min that foams down, promptly be prepared into foam materials.This invention has solved that the fragility that the melamino-formaldehyde foam materials of prior art exists is big, and snappiness is poor, the easy dry linting of foam, complicated process of preparation, and problems such as production cost height are with a wide range of applications.Meanwhile, also having a lot of melamino-formaldehyde foamy United States Patent (USP)s to be seen in reports for work.It is solidifying agent that US4666948 has proposed with 0.2%～4% basic metal, polyprotonic acid, co-polymeric acids, boric acid etc., prepares a kind of preparation method of elasticity melamino-formaldehyde foam materials.US5413853 has proposed a kind of melamino-formaldehyde foamy preparation technology and it has been carried out the method for hydrophobically modified.US5436278 adopts the mode of adding isocyanic ester in foaming process, has both improved the original brittle problem of melamino-formaldehyde foam, does not also reduce the flame retardant type and the heat insulating ability of melamino-formaldehyde have good lather simultaneously.US6607817 has proposed to add in the terpolycyantoamino-formaldehyde resin foaming process and has hated oil base group, prepares the method for the novel melamine-formaldehyde foam materials with oil-proofness.US20100144913 has proposed a kind of germ resistance group that adds in the melamino-formaldehyde performed polymer, prepare the method for the novel melamine-formaldehyde foam materials with germ resistance.
The research of cyanurotriamide modified urea resin foam materials aspect at present is not seen in report as yet.
Summary of the invention
Technical problem:In order to solve good inadequately, the bad shortcoming of water tolerance of flame retardant resistance that prior art exists, the invention provides a kind of high preparation method who contains the expandability cyanurotriamide modified urea resin admittedly, have the advantage of water-tolerant, foam materials intensity height, good flame resistance.
Technical scheme:A kind of high preparation method who contains the expandability cyanurotriamide modified urea resin admittedly, preparation process is:
The first step adds reactor with formaldehyde solution, Paraformaldehyde 96, is warming up to 80 ℃～90 ℃, and regulating the pH value is 7.0～10.0, adds urea and trimeric cyanamide, reaction 20～40min;
Second step, regulate pH value to 4.0～6.9, under 80 ℃～90 ℃ conditions, react, until cloud point occurring;
The 3rd step, regulate pH value to 5.0～6.9, add urea and trimeric cyanamide, under 80 ℃～90 ℃ conditions, react 20～50min;
The 4th step, regulate pH value to 7.0～10.0, add trimeric cyanamide, be cooled to 90 ℃～70 ℃ simultaneously, reaction 10～30min;
The 5th step under 60 ℃～70 ℃ conditions, added urea, was cooled to 50 ℃～60 ℃, reaction 10～20min;
The add-on of Paraformaldehyde 96 is 70%～75% of formaldehyde solution and a Paraformaldehyde 96 total mass, the total mass that adds urea is that the mass ratio of the urea that adds of 40%～45%, three times of the total adding quality of formaldehyde solution, Paraformaldehyde 96, urea, trimeric cyanamide is 3～5:1:1; It is that the mass ratio of the trimeric cyanamide that adds of 10%～25%, three times of the total adding quality of formaldehyde solution, Paraformaldehyde 96, urea, trimeric cyanamide is 1:1:6 that trimeric cyanamide always adds quality.
The first step that adjusting pH value adopts respectively is that mass concentration is 30%～60% strong alkaline aqueous solution, and second step was that mass concentration is 15%～25% weakly acidic water solution, and third and fourth step is that mass concentration is 10%～30% strong alkaline aqueous solution.
Beneficial effect:
The present invention adopts progressively copolymerization process to prepare height to contain the expandability cyanurotriamide modified urea resin admittedly, adopt progressively copolycondensation mode, under the pH of alkali-acid-alkali value condition, urea and trimeric cyanamide progressively add in batches, formaldehyde and urea, trimeric cyanamide are fully reacted, reduce free formaldehyde content, simultaneously owing to add trimeric cyanamide, generate melamine methylol, make that the free formaldehyde content in the urea-formaldehyde resin further descends.
The present invention by Paraformaldehyde 96 depolymerization under alkaline condition, obtains highly concentrated formaldehyde solution in building-up process, with urea, trimeric cyanamide reaction, directly prepare height and contain the expandability cyanurotriamide modified urea resin admittedly.Avoided dehydration and administered the environmental pollution that the waste water process causes, reduced cost greatly simultaneously.
The present invention adopts trimeric cyanamide in the copolycondensation process urea-formaldehyde resin to be carried out modification, in the urea-formaldehyde resin molecule, introduce trimeric cyanamide, owing to formed tridimensional network, can seal many water-absorbent groups, simultaneously trimeric cyanamide show alkalescence can in and the acid in the resin, prevent and reduced the degraded and the hydrolysis rate of resin to a certain extent, thereby improve the water tolerance of urea-formaldehyde resin.Simultaneously, add flame retardant resistance and the thermostability that trimeric cyanamide can improve urea-formaldehyde resin greatly.
The cyanurotriamide modified urea resin foam materials had both had urea formaldehyde condensate foam cheapness, lightweight, the fireballing advantage of foaming, had advantages such as the melamino-formaldehyde foam materials is fire-retardant, water-fast, physical strength is good simultaneously again.The present invention utilizes trimeric cyanamide that the urea-formaldehyde resin of low mol ratio is carried out modification, by reducing hydroxymethyl ether linkage content in the resin structure, increase triazine ring structure, increase the urea-formaldehyde resin molecular structure the polymerization degree, increase its water tolerance, increase the intensity and the flame retardant type of foam materials simultaneously, increased its range of application greatly.
Embodiment
A kind of high preparation method who contains the expandability cyanurotriamide modified urea resin admittedly, preparation process is:
The first step adds reactor with formaldehyde solution, Paraformaldehyde 96, is warming up to 80 ℃～90 ℃, and regulating its pH value with the strong alkaline aqueous solutions such as NaOH, KOH of 30%～60% concentration is 7.0～10.0.The purpose of doing like this is to make Paraformaldehyde 96 depolymerization under alkaline condition obtain mass concentration to be 50%～70% highly concentrated formaldehyde solution, to prepare the expandable resin of high solids content again with this.Then, add first urea and first trimeric cyanamide again, reaction 20～40min;
Second step is with the NH of 15%～25% concentration
4Weakly acidic water such as Cl, oxalic acid solution is regulated pH value to 4.0～6.9, reacts under 80 ℃～90 ℃ conditions, and until cloud point occurring, this reactions steps time is 20～60min;
The 3rd step, regulate pH value to 5.0～6.9 with the strong alkaline aqueous solutions such as NaOH, KOH of 10%～30% concentration, add second batch of urea and second batch of trimeric cyanamide, under 80 ℃～90 ℃ conditions, react 20～50min;
The 4th step, regulate pH value to 7.0～10.0 with the strong alkaline aqueous solutions such as NaOH, KOH of 10%～30% concentration, add the 3rd batch of trimeric cyanamide, be cooled to 90 ℃～70 ℃ simultaneously, reaction 10～30min;
The 5th step under 60 ℃～70 ℃ conditions, added the 3rd batch of urea, was cooled to 50 ℃～60 ℃, reaction 10～20min.
The add-on of Paraformaldehyde 96 is 70%～75% of formaldehyde solution and a Paraformaldehyde 96 total mass, is controlled at 70wt%～80 wt % with the solid content that guarantees whole system, contains the expandability cyanurotriamide modified urea resin admittedly thereby directly obtain height; Urea divides three batches of addings, and the total add-on of urea is that the ratio between formaldehyde solution, Paraformaldehyde 96, urea, the total add-on of trimeric cyanamide 40%～45%, three batches is 3～5:1:1; Trimeric cyanamide divides three batches of addings, and the total add-on of trimeric cyanamide is that the ratio between formaldehyde solution, Paraformaldehyde 96, urea, the total add-on of trimeric cyanamide 10%～25%, three batches is 1:1:6.
It is respectively that the first step is that mass concentration is 30%～60% the NaOH aqueous solution that the pH value is regulated, and second step was that mass concentration is 15%～25% NH
4The Cl aqueous solution, third and fourth step is that mass concentration is 10%～30% the NaOH aqueous solution.
The pH value conditioning agent that is adopted in following examples comprises that mass concentration is a 50%NaOH solution; The NH of 20% mass concentration
4Cl solution; The NaOH solution of 15% mass concentration.About concentration of formaldehyde: existing commercially available formaldehyde solution concentration is all between 35～37%, and the concentration of mentioning among the embodiment of separating the formaldehyde solution of using in the collecting process at Paraformaldehyde 96 is 36.8%wt.Paraformaldehyde 96 is a powdery solid, and massfraction is 95%.
Embodiment 1
1): 66.1g formaldehyde solution, 160.5g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 90 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.0, adds first urea 168g, first trimeric cyanamide 15g, reaction 30min;
2): with the NH of 20% concentration
4Cl solution is regulated pH value to 5.8, reacts under 90 ℃ of conditions, and until cloud point occurring, this reactions steps time is about 30min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.6, adds second crowd of urea 48g, and second crowd of trimeric cyanamide 15g reacts 40min under 90 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.5, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 70 ℃ simultaneously, reaction 20min;
5): under 70 ℃ of conditions, add the 3rd crowd of urea 48g, be cooled to 60 ℃, reaction 15min, postcooling discharging.
Embodiment 2
1): 63.5g formaldehyde solution, 165g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 90 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.3, adds first urea 168g, first trimeric cyanamide 15g, reaction 30min;
2): with the NH of 20% concentration
4Cl solution is regulated pH value to 6.5, under 90 ℃ of conditions, react, until occur cloud point to, this reactions steps time is 60min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.5, adds second crowd of urea 48g, and second crowd of trimeric cyanamide 15g reacts 40min under 90 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.0, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 70 ℃ simultaneously, reaction 20min;
5): under 70 ℃ of conditions, add the 3rd crowd of urea 48g, be cooled to 60 ℃, reaction 15min, postcooling discharging.
Embodiment 3
1): 70g formaldehyde solution, 157.5g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 90 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.2, adds first urea 164g, first trimeric cyanamide 15g, reaction 30min;
2): regulate pH value to 6.2 with the NH4Cl solution of 20% concentration, under 90 ℃ of conditions, react, until occur cloud point to, this reactions steps time is 40min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.6, adds second crowd of urea 50g, and second crowd of trimeric cyanamide 15g reacts 40min under 90 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.5, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 70 ℃ simultaneously, reaction 20min;
5): under 70 ℃ of conditions, add the 3rd crowd of urea 50g, be cooled to 60 ℃, reaction 15min, postcooling discharging.
Embodiment 4
1): 64g formaldehyde solution, 166.5g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 90 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.3, adds first urea 168g, first trimeric cyanamide 15g, reaction 30min;
2): with the NH of 20% concentration
4Cl solution is regulated pH value to 5.9, under 90 ℃ of conditions, react, until occur cloud point to, this reactions steps time is 33min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.7, adds second crowd of urea 48g, and second crowd of trimeric cyanamide 15g reacts 40min under 90 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.2, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 70 ℃ simultaneously, reaction 20min;
5): under 70 ℃ of conditions, add the 3rd crowd of urea 48g, be cooled to 60 ℃, reaction 15min, postcooling discharging.
Embodiment 5
1): 66.1g formaldehyde solution, 160.5g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 90 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.4, adds first urea 168g, first trimeric cyanamide 15g, reaction 30min;
2): with the NH of 20% concentration
4Cl solution is regulated pH value to 5.7, under 90 ℃ of conditions, react, until occur cloud point to, this reactions steps time is 36min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.6, adds second crowd of urea 48g, and second crowd of trimeric cyanamide 15g reacts 40min under 90 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.5, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 70 ℃ simultaneously, reaction 20min;
5): under 70 ℃ of conditions, add the 3rd crowd of urea 48g, be cooled to 60 ℃, reaction 15min, postcooling discharging.
Embodiment 6
1): 64g formaldehyde solution, 160g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 90 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.5, adds first urea 170g, first trimeric cyanamide 15g, reaction 30min;
2): with the NH of 20% concentration
4Cl solution is regulated pH value to 5.4, under 90 ℃ of conditions, react, until occur cloud point to, this reactions steps time is 50min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.5, adds second crowd of urea 49g, and second crowd of trimeric cyanamide 15g reacts 40min under 90 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.2, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 70 ℃ simultaneously, reaction 20min;
5): under 70 ℃ of conditions, add the 3rd crowd of urea 49g, be cooled to 60 ℃, reaction 15min, postcooling discharging.
Embodiment 7
1): 65g formaldehyde solution, 160g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 88 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.9, adds first urea 170g, first trimeric cyanamide 15g, reaction 30min;
2): with the NH of 20% concentration
4Cl solution is regulated pH value to 5.5, under 90 ℃ of conditions, react, until occur cloud point to, this reactions steps time is 40min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.4, adds second crowd of urea 47g, and second crowd of trimeric cyanamide 15g reacts 40min under 91 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.2, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 80 ℃ simultaneously, reaction 20min;
5): under 75 ℃ of conditions, add the 3rd crowd of urea 47g, be cooled to 65 ℃, reaction 15min, postcooling discharging.
Embodiment 8
1): 66g formaldehyde solution, 162g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 90 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.3, adds first urea 171g, first trimeric cyanamide 15g, reaction 30min;
2): with the NH of 20% concentration
4Cl solution is regulated pH value to 5.6, under 90 ℃ of conditions, react, until occur cloud point to, this reactions steps time is 25min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.6, adds second crowd of urea 47g, and second crowd of trimeric cyanamide 15g reacts 40min under 90 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.6, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 70 ℃ simultaneously, reaction 20min;
5): under 70 ℃ of conditions, add the 3rd crowd of urea 47g, be cooled to 60 ℃, reaction 15min, postcooling discharging.
Embodiment 9
1): 65g formaldehyde solution, 160g Paraformaldehyde 96 are added the 1000ml reactor, be warming up to 90 ℃, regulating its pH value with the NaOH solution of 50% concentration is 8.4, adds first urea 168g, first trimeric cyanamide 15g, reaction 30min;
2): with the NH of 20% concentration
4Cl solution is regulated pH value to 5.9, under 90 ℃ of conditions, react, until occur cloud point to, this reactions steps time is 35min;
3): the NaOH solution with 15% concentration is regulated pH value to 6.7, adds second crowd of urea 48g, and second crowd of trimeric cyanamide 15g reacts 40min under 90 ℃ of conditions;
4): the NaOH solution with 15% concentration is regulated pH value to 8.8, adds the 3rd crowd of trimeric cyanamide 90g, is cooled to 70 ℃ simultaneously, reaction 20min;
5): under 70 ℃ of conditions, add the 3rd crowd of urea 48g, be cooled to 60 ℃, reaction 15min, postcooling discharging.
The height of subordinate list 1 different ingredients contains the performance of expandability cyanurotriamide modified urea resin and foam materials thereof admittedly
| Prescription | Solid content/% | Viscosity/mpa.s | Free formaldehyde content/% | Methylol group content/% | Oxygen index/% | Apparent density/g/cm 3 |
| Embodiment 1 | 74 | 1050 | 0.15 | 31.2 | 61 | 0.036 |
| Embodiment 2 | 76 | 1100 | 0.20 | 34.2 | 54 | 0.042 |
| Embodiment 3 | 72 | 950 | 0.12 | 29.5 | 65 | 0.031 |
| Embodiment 4 | 75 | 1050 | 0.19 | 34.9 | 57 | 0.041 |
| Embodiment 5 | 74 | 1150 | 0.14 | 31.5 | 60 | 0.032 |
| Embodiment 6 | 73 | 1020 | 0.17 | 33.6 | 59 | 0.033 |
| Embodiment 7 | 73 | 1000 | 0.16 | 33.2 | 60 | 0.031 |
| Embodiment 8 | 72 | 900 | 0.14 | 32.5 | 62 | 0.041 |
| Embodiment 9 | 74 | 1050 | 0.15 | 33.5 | 57 | 0.038 |
The present invention prepares height, and to contain expandability cyanurotriamide modified urea resin solid content admittedly be 70%～80%, and viscosity is 800～1200mpa.s, and free formaldehyde content is 0.1%～0.25%.The cyanurotriamide modified urea resin foam materials apparent density that obtains through foaming reaches 0.03g/cm
3～0.05g/cm
3, oxygen index is 50%～70%, has reached the requirement of lightweight, fire-retardant building material, for the development and utilization of anti-flaming environment-friendly urea-formaldehyde resin cellular insulant provides new approach.
Claims (2)
1. one kind high preparation method who contains the expandability cyanurotriamide modified urea resin admittedly is characterized in that preparation process is:
The first step adds reactor with formaldehyde solution, Paraformaldehyde 96, is warming up to 80 ℃～90 ℃, and regulating the pH value is 7.0～10.0, adds urea and trimeric cyanamide, reaction 20～40min;
Second step, regulate pH value to 4.0～6.9, under 80 ℃～90 ℃ conditions, react, until cloud point occurring;
The 3rd step, regulate pH value to 5.0～6.9, add urea and trimeric cyanamide, under 80 ℃～90 ℃ conditions, react 20～50min;
The 4th step, regulate pH value to 7.0～10.0, add trimeric cyanamide, be cooled to 90 ℃～70 ℃ simultaneously, reaction 10～30min;
The 5th step under 60 ℃～70 ℃ conditions, added urea, was cooled to 50 ℃～60 ℃, reaction 10～20min;
The add-on of Paraformaldehyde 96 is 70%～75% of formaldehyde solution and a Paraformaldehyde 96 total mass, the total mass that adds urea is that the mass ratio of the urea that adds of 40%～45%, three times of the total adding quality of formaldehyde solution, Paraformaldehyde 96, urea, trimeric cyanamide is 3～5:1:1; It is that the mass ratio of the trimeric cyanamide that adds of 10%～25%, three times of the total adding quality of formaldehyde solution, Paraformaldehyde 96, urea, trimeric cyanamide is 1:1:6 that trimeric cyanamide always adds quality.
2. height according to claim 1 contains the preparation method of expandability cyanurotriamide modified urea resin admittedly, it is characterized in that, the first step that adjusting pH value adopts respectively is that mass concentration is 30%～60% strong alkaline aqueous solution, second step was that mass concentration is 15%～25% weakly acidic water solution, and third and fourth step is that mass concentration is 10%～30% strong alkaline aqueous solution.
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| CN103132397A (en) * | 2011-11-24 | 2013-06-05 | 大亚科技股份有限公司 | Manufacturing method for washing machine cover plate purpose density fiberboards |
| CN103641970A (en) * | 2013-12-04 | 2014-03-19 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high-solid-content melamino-formaldehyde-base resin |
| CN104559051A (en) * | 2014-12-29 | 2015-04-29 | 中科院广州化学有限公司 | Intrinsic flame-retardant bi-component modified melamine formaldehyde foam as well as preparation method and applications thereof |
| CN104774298A (en) * | 2014-05-23 | 2015-07-15 | 嘉兴市杭星精细化工有限公司 | Production technology of amino resin with ultralow free formaldehyde content |
| CN107987766A (en) * | 2017-12-14 | 2018-05-04 | 南京林业大学 | A kind of method that biomass adhesive is prepared using formaldehyde slag |
| CN114220667A (en) * | 2021-12-31 | 2022-03-22 | 福州大学 | Hollow nickel hydroxide needle-punched microsphere electrode material and preparation method and application thereof |
| CN115368525A (en) * | 2022-08-21 | 2022-11-22 | 广西精典化工新材料有限公司 | Method for synthesizing environment-friendly urea-formaldehyde resin by using paraformaldehyde |
| CN115819696A (en) * | 2022-10-26 | 2023-03-21 | 福州大学 | Low-free-formaldehyde melamine formaldehyde resin with antibacterial property and preparation method thereof |
| CN116874710A (en) * | 2022-08-29 | 2023-10-13 | 江苏长顺高分子材料研究院有限公司 | Flame-retardant polyurethane rigid foam, preparation method and application thereof |
| CN116874702A (en) * | 2022-08-29 | 2023-10-13 | 江苏长顺高分子材料研究院有限公司 | Modified urea-formaldehyde resin, preparation method and application thereof |
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| CN101302412A (en) * | 2008-06-13 | 2008-11-12 | 西南林学院 | Melamine-urea-methyl aldehyde copolycondensation resin lumber adhesive and preparation thereof |
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| CN101302412A (en) * | 2008-06-13 | 2008-11-12 | 西南林学院 | Melamine-urea-methyl aldehyde copolycondensation resin lumber adhesive and preparation thereof |
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| 《林业工业》 20081231 朱丽滨 三聚氰胺改性低毒脲醛树脂耐水性研究 19-22以及33 1-2 第35卷, 第2期 * |
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| CN103132397A (en) * | 2011-11-24 | 2013-06-05 | 大亚科技股份有限公司 | Manufacturing method for washing machine cover plate purpose density fiberboards |
| CN103132397B (en) * | 2011-11-24 | 2015-06-17 | 大亚人造板集团有限公司 | Manufacturing method for washing machine cover plate purpose density fiberboards |
| CN103641970A (en) * | 2013-12-04 | 2014-03-19 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high-solid-content melamino-formaldehyde-base resin |
| CN103641970B (en) * | 2013-12-04 | 2015-07-29 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of high-solid-content melamino-formaldehydresine resine |
| CN104774298A (en) * | 2014-05-23 | 2015-07-15 | 嘉兴市杭星精细化工有限公司 | Production technology of amino resin with ultralow free formaldehyde content |
| CN104774298B (en) * | 2014-05-23 | 2017-12-08 | 浙江亚迪纳新材料科技股份有限公司 | A kind of production technology of super Amino Group Resin Containing Low Free Formaldehyde |
| CN104559051A (en) * | 2014-12-29 | 2015-04-29 | 中科院广州化学有限公司 | Intrinsic flame-retardant bi-component modified melamine formaldehyde foam as well as preparation method and applications thereof |
| CN104559051B (en) * | 2014-12-29 | 2017-01-11 | 中科院广州化学有限公司 | Intrinsic flame-retardant bi-component modified melamine formaldehyde foam as well as preparation method and applications thereof |
| CN107987766A (en) * | 2017-12-14 | 2018-05-04 | 南京林业大学 | A kind of method that biomass adhesive is prepared using formaldehyde slag |
| CN107987766B (en) * | 2017-12-14 | 2020-09-11 | 南京林业大学 | Method for preparing biomass adhesive by using formaldehyde residues |
| CN114220667A (en) * | 2021-12-31 | 2022-03-22 | 福州大学 | Hollow nickel hydroxide needle-punched microsphere electrode material and preparation method and application thereof |
| CN114220667B (en) * | 2021-12-31 | 2023-12-12 | 福州大学 | Hollow nickel hydroxide needled microsphere electrode material and preparation method and application thereof |
| CN115368525A (en) * | 2022-08-21 | 2022-11-22 | 广西精典化工新材料有限公司 | Method for synthesizing environment-friendly urea-formaldehyde resin by using paraformaldehyde |
| CN116874710A (en) * | 2022-08-29 | 2023-10-13 | 江苏长顺高分子材料研究院有限公司 | Flame-retardant polyurethane rigid foam, preparation method and application thereof |
| CN116874702A (en) * | 2022-08-29 | 2023-10-13 | 江苏长顺高分子材料研究院有限公司 | Modified urea-formaldehyde resin, preparation method and application thereof |
| CN115819696A (en) * | 2022-10-26 | 2023-03-21 | 福州大学 | Low-free-formaldehyde melamine formaldehyde resin with antibacterial property and preparation method thereof |
| CN115819696B (en) * | 2022-10-26 | 2024-08-23 | 福州大学 | Low free formaldehyde melamine formaldehyde resin with antibacterial property and preparation method thereof |
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