CN102675575B - Preparation method of melamine formaldehyde resin for foam - Google Patents
Preparation method of melamine formaldehyde resin for foam Download PDFInfo
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- CN102675575B CN102675575B CN 201210128145 CN201210128145A CN102675575B CN 102675575 B CN102675575 B CN 102675575B CN 201210128145 CN201210128145 CN 201210128145 CN 201210128145 A CN201210128145 A CN 201210128145A CN 102675575 B CN102675575 B CN 102675575B
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Abstract
The invention discloses a preparation method of melamine formaldehyde resin for foam, which comprises the following steps: adding alkali into formaldehyde solution, adjusting the pH value to be 8.0-10 and uniformly agitating; adding a buffer agent, wherein the addition quantity of the buffer agent is 2-10 percent of the total weight of resin; adding melamine, controlling the molar ratio of the melamine to formaldehyde to be 1:(1-4), subsequently adding a modifying agent, controlling the addition quantity of the modifying agent to be 0-30 percent of the dosage of the melamine, raising the temperature to 80-100 DEG C and carrying out heat preservation for 30-60 minutes, so that the water soluble multiple is 1-2; adding a stabilizing agent, controlling the dosage of the stabilizing agent to be 5-10 percent of the total weight of the resin and cooling to obtain the melamine formaldehyde resin, wherein the prepared melamine formaldehyde resin has a solid content of 40-80 percent (by weight) and a viscosity of 50-200 mPa.s (25-45 DEG C) and can be stored for more than 30 days at room temperature. The foam generated by using the synthesized melamine formaldehyde modified resin has good mechanical strength and flame-retardant property.
Description
Technical field
The invention belongs to chemical field, relate to a kind of production technique of material, particularly a kind of foam preparation method of terpolycyantoamino-formaldehyde resin.
Background technology
The foam materials of terpolycyantoamino-formaldehyde resin preparation has good flame retardancy, thermostability, ageing-resistant performance and heat-insulating property.But also can be easy to dye, aftertreatment such as cutting processing.It is the fire-retardant novel material of a kind of novel environment friendly that present industry is generally acknowledged.The terpolycyantoamino-formaldehyde resin froth product has progressively begun to apply in fields such as building, machinery, chemical industry, communications and transportation.
As the base-material of making the terpolycyantoamino-formaldehyde resin foam, the fundamental property of terpolycyantoamino-formaldehyde resin directly influences the final performance of terpolycyantoamino-formaldehyde resin foam.Make at present the most general problem of terpolycyantoamino-formaldehyde resin foam and be except the melamine foam brittleness is big, the resilience difference, also exist the problem for the terpolycyantoamino-formaldehyde resin poor storage stability of foam production.In order to reduce melamine resin moisture content to the influence of foaming, produce the melamine foam generally all adopt high solid content, than the terpolycyantoamino-formaldehyde resin of low polymerization degree.In fact, contain a large amount of trimeric cyanamide methylol low-molecular materials than the terpolycyantoamino-formaldehyde resin of low polymerization degree, in storage process, terpolycyantoamino-formaldehyde resin is easy to take place polymerization, clouding, precipitation occur even solidifies.Terpolycyantoamino-formaldehyde resin foam patents such as China document CN1831023, CN101423648, CN102086270A, CN101415757A are just mentioned with terpolycyantoamino-formaldehyde resin and are produced foam, all do not mention the preparation method of terpolycyantoamino-formaldehyde resin and the stability problem of resin.China document CN1903905A has described a kind of highly filled melmac production method.Described the method that single stage method is produced highly filled terpolycyantoamino-formaldehyde resin, how not controlled terpolycyantoamino-formaldehyde resin and react to prepare stable terpolycyantoamino-formaldehyde resin report but relate to.China document CN101671472A has reported that the terpolycyantoamino-formaldehyde resin storge quality is good, grows problem working life.But terpolycyantoamino-formaldehyde resin solution time working life that this patent system gets can only guarantee 72 hours, and the resin viscosity increase is very fast as can be seen from the data announced, can not guarantee the resin stable storing.
The invention discloses and a kind ofly effectively control the level of response of trimeric cyanamide and formaldehyde by add buffer reagent in trimeric cyanamide and formaldehyde reaction process, the while is being reacted latter stage adding stablizer, the stability that prolongs terpolycyantoamino-formaldehyde resin greatly.The terpolycyantoamino-formaldehyde resin solution shelf lives of the present invention's preparation can reach (25 ℃) more than 30 days.The terpolycyantoamino-formaldehyde resin foam that the terpolycyantoamino-formaldehyde resin that makes with the inventive method is produced has the satisfactory stability performance.
Summary of the invention
Technical problem:It is bad with the terpolycyantoamino-formaldehyde resin stability in storage to solve existing melamine foam, and the synthetic big shortcoming of terpolycyantoamino-formaldehyde resin performance difference of same production technique, the invention provides a kind of manufacture method of using terpolycyantoamino-formaldehyde resin by the foam that in resin reaction, adds buffer reagent, properties-correcting agent, stablizer synthesizing stable.
Technical scheme:A kind of foam comprises the steps: with the preparation method of terpolycyantoamino-formaldehyde resin
(1), alkali is added formaldehyde solution, regulate pH=8.0 ~ 10.0, stir; Add buffer reagent, the add-on of buffer reagent is 2 ~ 10%(weight ratio of total resin weight);
(2), add trimeric cyanamide, the mol ratio of trimeric cyanamide and formaldehyde adds properties-correcting agent subsequently between 1:1 ~ 4, the add-on of properties-correcting agent be the trimeric cyanamide consumption 0～30% between (weight ratio), be warming up to 80～100 ℃, insulation 30 ~ 60min, making water-soluble multiple is 1 ~ 2;
(3), add stablizer, the consumption of stablizer is 5～10%(parts by weight of total resin weight), cooling obtains terpolycyantoamino-formaldehyde resin.Resin solid content is 40 ~ 80% (wt), and 25-45 ℃ of following viscosity is 50 ~ 200mPa.s.
Alkali is NaOH, KOH, Na in the described step (1)
2CO
3, NaHCO
3In one or more, preferably regulate pH=8.5-9.5.
Buffer reagent is selected one or more in Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, trolamine, the diethanolamine in the described step (1).
The mol ratio of preferred trimeric cyanamide and formaldehyde is warming up to 85～95 ℃ in the described step (2) between 1:2～2.5, insulation 30min, and water-soluble multiple is 1.5.
Properties-correcting agent is one or more in methyl substituted trimeric cyanamide, benzoguanamine, Dyhard RU 100, phenol, the urea in the described step (2).
The speed control that heats up in the described step (2) is at 1.5～2.5 ℃/minute.
Described heat-up rate is preferably controlled at 2 ℃/minute.
Stablizer is selected one or more in ethylene glycol, Diethylene Glycol, glycerol, butanols, ethanol, butyleneglycol, the amylalcohol in the described step (3).
A kind of foam terpolycyantoamino-formaldehyde resin, wherein resin solid content is 40 ~ 80% (wt), 25-45 ℃ of following viscosity is 50 ~ 200mPa.s.
A kind of preparation method of terpolycyantoamino-formaldehyde resin foam, 100 parts of terpolycyantoamino-formaldehyde resins of foam by method for preparing, add 1.5 parts of OP-10,18 parts of sherwood oils, 3 parts in formic acid (described " part " is mass parts), foamable is 60 seconds in microwave, obtain the terpolycyantoamino-formaldehyde resin foam, the terpolycyantoamino-formaldehyde resin foam density is 7 ~ 12kg/m
3, tensile strength is 0.01 ~ 0.04MPa.
The ultimate principle that the present invention prepares stable terpolycyantoamino-formaldehyde resin is:
Disproportionation reaction can take place and cause system pH to descend rapidly in formaldehyde under the highly basic condition, especially this reaction is rapider after the rising temperature.React the melamino-formaldehyde reaction product difference that pH descends the general who has surrendered to cause different time to be produced rapidly, cause the poor repeatability of resin property.
Formaldehyde disproportionation reaction: 2HCHO+NaOH---HCOONa+CH
3OH
According to these characteristics of formaldehyde, the present invention is chosen in the pH of adjusting formaldehyde solution under the room temperature 8.5～9.0, adds buffer reagent stabilising system acidity, adds trimeric cyanamide again, and the rising temperature of reaction reduces the formaldehyde disproportionation reaction to greatest extent and takes place.
Trimeric cyanamide and formaldehyde reaction are subjected to the influence of pH very big, and in different pH scopes, synthetic product is different, and constantly the pH that changes will cause the difference of resin product.Therefore will obtain the terpolycyantoamino-formaldehyde resin of stable performance, it is particularly important that stabilising system pH seems.Add buffer reagent effectively the pH of the hierarchy of control in a very little scope.The buffer reagent that evidence the present invention mentions is effective.
The storge quality of melamine resin has direct relation with molecular weight size, molecular weight distribution, the molecular structure of melamine resin.Reach 200mPas(25 ℃ at the resin final viscosity) after, in the storage process, the speed that resin viscosity increases can be accelerated, add a spot of stablizer, not only can reduce the viscosity of resin, the frost resistance of raising resin, increase the hydrophilicity of resin, and can prolong the shelf lives of resin greatly.
Beneficial effect:The present invention adds stablizer, the stability that prolongs terpolycyantoamino-formaldehyde resin greatly at the reaction latter stage simultaneously by add the level of response that buffer reagent is effectively controlled trimeric cyanamide and formaldehyde in trimeric cyanamide and formaldehyde reaction process.The terpolycyantoamino-formaldehyde resin solution shelf lives of the present invention's preparation can reach (25 ℃) more than 30 days.The terpolycyantoamino-formaldehyde resin foam that the terpolycyantoamino-formaldehyde resin that makes with the inventive method is produced has the satisfactory stability performance.
Embodiment
The embodiment of the invention given below just is further described specifically the present invention.It is important to point out that embodiment only for the present invention is further elaborated, can not be interpreted as limiting the scope of the invention.Present embodiment is done an amount of improvement or change, still belong to protection scope of the present invention.
" part " of the following stated is mass parts.
Embodiment 1
Industrial formol solution 1250g with 37wt%, add and have thermometer, in the reactor of agitator and reflux exchanger, start stirring, regulate pH=8.0 in room temperature with sodium bicarbonate, add buffer reagent trolamine 22.5g again, trimeric cyanamide 1000g(trimeric cyanamide and formaldehyde mole ratio are 1:1.9), be raised to 90 ℃ of insulation reaction after 30 minutes by 2 ℃ of/minute heat-up rates, begin to test the water-soluble multiple of resin, up to the water-soluble multiple of resin reach 1 times (in the 10ml test tube, add the 1ml resin, add 1ml water again after, rocking resin presents transparent), add stablizer Diethylene Glycol 112.5g, continue reaction 30 minutes, cooling.Obtain the water white transparency thick liquid.Resin solid content 55wt%.Viscosity 55.9mPa.s (25 ℃), normal temperature storage is 178.90 mPa.s (25 ℃) after 30 days.
With 100 parts of above-mentioned synthetic resins, 1.5 parts of OP-10 of adding, 18 parts of sherwood oils, 3 parts in formic acid, foamable is 60 seconds in microwave, obtains the terpolycyantoamino-formaldehyde resin foam density: 8.5 kg/m
3, tensile strength: 0.0198MPa(normal temperature storage 2 days); Terpolycyantoamino-formaldehyde resin foam density 8.0kg/m
3, tensile strength: 0.0188MPa(normal temperature storage 30 days).
Embodiment 2
Formaldehyde solution 1250g with 37wt%, add and have thermometer, in the reactor of agitator and reflux exchanger, stir, regulate pH=9.5 in room temperature with potassium hydroxide, add buffer reagent Sodium phosphate dibasic 8g again, SODIUM PHOSPHATE, MONOBASIC 10g, trimeric cyanamide 850g(trimeric cyanamide and formaldehyde mole ratio are 1:2.27), properties-correcting agent benzoguanamine 250g, be warmed up to 80 ℃ of insulation reaction after 60 minutes by 2 ℃ of/minute heat-up rates, begin to test water-soluble multiple, up to the water-soluble multiple of resin reach 1.5 times (in the 10ml test tube, add the 1ml resin, add 1.5ml water again after, rock resin and present transparent), add stablizer ethylene glycol 55.9g, amylalcohol 50.0g, continue reaction 30 minutes, cooling obtains the water white transparency thick liquid.Resin solid content 54wt%.Viscosity 68.3mPa.s (25 ℃), normal temperature storage is 163.1 mPa.s (25 ℃) after 30 days.
With 100 parts synthetic of resins, 1.5 parts of OP-10 of adding, 18 parts of sherwood oils, 3 parts in formic acid, foamable is 60 seconds in microwave, obtains terpolycyantoamino-formaldehyde resin foam density: 9.1kg/m
3, tensile strength: 0.0356MPa(normal temperature storage 2 days); Terpolycyantoamino-formaldehyde resin foam density: 8.8kg/m
3, tensile strength: 0.0326MPa(normal temperature storage 30 days).
Embodiment 3
Industrial formol solution 1250g with 37wt%, add and have thermometer, in the reactor of agitator and reflux exchanger, stir, at room temperature regulate pH=10.0 with sodium hydroxide, add buffer reagent diethanolamine 20g again, trimeric cyanamide 648g(trimeric cyanamide and formaldehyde mole ratio are 1:3.0), properties-correcting agent Dyhard RU 100 47.3g, methyl substituted trimeric cyanamide 50.0g, be warmed up to 100 ℃ of insulations according to 2 ℃ of/minute heat-up rates, react after 30 minutes, begin to test the water-soluble multiple of resin, reach 2.0 times up to the water-soluble multiple of resin and (in the 10ml test tube, add the 1ml resin, after adding 2.0ml water again, rocking resin presents transparent), add stablizer glycerol 85.0g, continue reaction 30 minutes, cooling obtains the water white transparency thick liquid.Resin solid content 42wt%.Viscosity 53.7mPa.s (25 ℃), normal temperature storage is 114.4 mPa.s (25 ℃) after 30 days.
With 100 parts of above-mentioned synthetic resins, add 3 parts of 1.5 parts of OP-10, sherwood oil 18 weight parts, formic acid, foamable is 60 seconds in microwave, obtains the terpolycyantoamino-formaldehyde resin foam density: 10.1 kg/m
3, tensile strength: 0.0228MPa(normal temperature storage 2 days); Terpolycyantoamino-formaldehyde resin foam density: 9.9 kg/m
3, tensile strength: 0.0211MPa(normal temperature storage 30 days).
Embodiment 4
Industrial formol solution 1250g with 37wt%, add and have thermometer, in the reactor of agitator and reflux exchanger, stir, at room temperature regulate pH=8.5 with sodium hydroxide, add buffer reagent trolamine 18g again, trimeric cyanamide 648g(trimeric cyanamide and formaldehyde mole ratio are 1:3.0), add phenol 100g, be warmed up to 90 ℃ of insulations according to 1.5 ℃ of/minute heat-up rates, react after 45 minutes, begin to test the water-soluble multiple of resin, reach 1.0 times up to the water-soluble multiple of resin and (in the 10ml test tube, add the 1ml resin, after adding 1.0ml water again, rocking resin presents transparent), add stablizer butanols 85.0g, continue reaction 30 minutes, vacuum hydro-extraction, cooling obtains the melamino-formaldehyde solid resin.Resin solid content 75wt%.Viscosity 55.4mPa.s (45 ℃), normal temperature storage is 59.1 mPa.s (45 ℃) after 30 days.
With 100 parts of above-mentioned solid resins, 10 parts of OP-10 of adding, 18 parts of sherwood oil 60-90 degree, 8 parts in formic acid, (2.45GHZ) low fiery foamable is 3 minutes in the family expenses microwave, obtains the terpolycyantoamino-formaldehyde resin foam density: 8.5 kg/m
3, tensile strength: 0.0200MPa(normal temperature storage 2 days); Terpolycyantoamino-formaldehyde resin foam density: 8.9 kg/m
3, tensile strength: 0.0198MPa(normal temperature storage 30 days).
Embodiment 5
Industrial formol solution 1250g with 37wt%, add and have thermometer, in the reactor of agitator and reflux exchanger, stir, add Paraformaldehyde 96 500g, at room temperature adjust pH=8.5 with yellow soda ash, add buffer reagent SODIUM PHOSPHATE, MONOBASIC 36g again, trimeric cyanamide 486g(trimeric cyanamide and formaldehyde mole ratio are 1:4), properties-correcting agent urea 50g, be warmed up to 85 ℃ of insulations according to 2 ℃ of/minute heat-up rates, react after 30 minutes, begin to test the water-soluble multiple of resin, reach 1.8 times up to the water-soluble multiple of resin and (in the 10ml test tube, add the 1ml resin, after adding 1.8ml water again, rocking resin presents transparent), add stablizer butanols 68.9g, butyleneglycol 55.1g continues reaction 30 minutes, cooling obtains the water white transparency thick liquid.Resin solid content 65wt%.Viscosity 136.7mPa.s (25 ℃), normal temperature storage is 178.4 mPa.s (25 ℃) after 30 days.
With 100 parts of above-mentioned synthetic resins, 1.5 parts of OP-10 of adding, 18 parts of sherwood oils, 3 parts in formic acid, foamable is 60 seconds in microwave, obtains the terpolycyantoamino-formaldehyde resin foam density: 8.91 kg/m
3, tensile strength: 0.0198MPa(normal temperature storage 2 days); Terpolycyantoamino-formaldehyde resin foam density: 8.80 kg/m
3, tensile strength: 0.0209MPa(normal temperature storage 30 days).
Embodiment 6
Industrial formol solution 1250g with 37wt%, add and have thermometer, in the reactor of agitator and reflux exchanger, stir, at room temperature regulate pH=8～9 with sodium hydroxide, add buffer reagent trolamine 18g again, trimeric cyanamide 648g(trimeric cyanamide and formaldehyde mole ratio are 1:3.0), add properties-correcting agent Dyhard RU 100 125g, be warmed up to 95 ℃ of insulations according to 2.5 ℃ of/minute heat-up rates, react after 30 minutes, begin to test the water-soluble multiple of resin, reach 1.0 times up to the water-soluble multiple of resin and (in the 10ml test tube, add the 1ml resin, after adding 1.0ml water again, rocking resin presents transparent), add stabilizer alcohol 85.0g, continue reaction 30 minutes, vacuum hydro-extraction, cooling obtains the melamino-formaldehyde solid resin.Resin solid content 77wt%.Viscosity 24.8mPa.s (45 ℃), normal temperature storage is 28.9 mPa.s (45 ℃) after 30 days.
With 100 parts of above-mentioned solid resins, 10 parts of OP-10 of adding, 18 parts of sherwood oil 60-90 degree, 8 parts in formic acid, (2.45GHZ) low fiery foamable is 3 minutes in the family expenses microwave, obtains the terpolycyantoamino-formaldehyde resin foam density: 9.8 kg/m
3, tensile strength: 0.0188MPa(normal temperature storage 2 days); Terpolycyantoamino-formaldehyde resin foam density: 9.6 kg/m
3, tensile strength: 0.0179MPa(normal temperature storage 30 days).
Claims (5)
1. the preparation method of a foam usefulness terpolycyantoamino-formaldehyde resin is characterized in that comprising the steps:
(1), alkali is added formaldehyde solution, regulate pH=8.0 ~ 10.0, stir; Add buffer reagent, the add-on of buffer reagent is 2 ~ 10%(weight ratio of total resin weight);
(2), add trimeric cyanamide, the mol ratio of trimeric cyanamide and formaldehyde adds properties-correcting agent subsequently between 1:1 ~ 4, the add-on of properties-correcting agent be the trimeric cyanamide consumption 0～30% between (weight ratio), be warming up to 80～100 ℃, insulation 30 ~ 60min, making water-soluble multiple is 1 ~ 2;
(3), add stablizer, the consumption of stablizer is 5～10%(weight ratio of total resin weight), cooling obtains terpolycyantoamino-formaldehyde resin, resin solid content is 40 ~ 80% (wt), 25-45 ℃ of following viscosity is 50 ~ 200mPa.s;
Wherein: alkali is NaOH, KOH, Na in the described step (1)
2CO
3, NaHCO
3In one or more, regulate pH in 8.5～9.5 scopes;
Buffer reagent is selected one or more in Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, trolamine, the diethanolamine in the described step (1);
Stablizer is selected one or more in ethylene glycol, Diethylene Glycol, glycerol, butanols, ethanol, butyleneglycol, the amylalcohol in the described step (3).
2. foam according to claim 1 is with the preparation method of terpolycyantoamino-formaldehyde resin, it is characterized in that: the mol ratio of preferred trimeric cyanamide and formaldehyde is between 1:2～2.5 in the described step (2), be warming up to 85～95 ℃, insulation 30min, water-soluble multiple is 1.5.
3. foam according to claim 1 is with the preparation method of terpolycyantoamino-formaldehyde resin, and it is characterized in that: properties-correcting agent is one or more in methyl substituted trimeric cyanamide, benzoguanamine, Dyhard RU 100, phenol, the urea in the described step (2).
4. foam according to claim 1 is with the preparation method of terpolycyantoamino-formaldehyde resin, and it is characterized in that: the speed control that heats up in the described step (2) is at 1.5～2.5 ℃/minute.
5. foam according to claim 4 is with the preparation method of terpolycyantoamino-formaldehyde resin, and it is characterized in that: described heat-up rate control is at 2 ℃/minute.
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| CN 201210128145 CN102675575B (en) | 2012-04-28 | 2012-04-28 | Preparation method of melamine formaldehyde resin for foam |
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|---|---|---|---|
| CN 201210128145 CN102675575B (en) | 2012-04-28 | 2012-04-28 | Preparation method of melamine formaldehyde resin for foam |
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| CN102675575B true CN102675575B (en) | 2013-10-09 |
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| CN102961955B (en) * | 2012-11-26 | 2015-09-23 | 山东泰德新能源有限公司 | A kind of formaldehyde scavenger and preparation method thereof |
| CN103554404A (en) * | 2013-11-08 | 2014-02-05 | 东莞市华立实业股份有限公司 | Low-melamine formaldehyde resin and preparation method thereof |
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| CN104119488B (en) * | 2014-07-16 | 2015-11-18 | 南京林业大学 | The synthetic method of terpolycyantoamino-formaldehyde resin precipitation and the application as amine resin tackiness agent modifying agent thereof |
| CN104387542A (en) * | 2014-11-04 | 2015-03-04 | 崇州合瑞科技有限公司 | High-toughness and water-resistant modified melamine urea-formaldehyde resin |
| CN106279589A (en) * | 2015-09-25 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of synthetic method of melmac |
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| CN109971032B (en) * | 2019-04-09 | 2022-04-01 | 濮阳绿宇新材料科技股份有限公司 | High-flame-retardancy, hydrophobic and oleophobic melamine foam and preparation method and application thereof |
| CN110894272B (en) * | 2019-11-04 | 2022-09-13 | 圣象实业（江苏）有限公司 | Synthesis process of melamine resin for long-storage-period impregnation |
| CN111409154B (en) * | 2020-05-07 | 2021-07-06 | 广西祥盛家居材料科技股份有限公司 | Method for producing veneer shaving board |
| CN113667078B (en) * | 2021-09-02 | 2024-06-11 | 浙江宝时美化工有限公司 | Preparation method of modified amino resin |
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