CN110615880A - Epoxy compound and polyol prepolymer modified urea-formaldehyde resin and preparation method thereof - Google Patents
Epoxy compound and polyol prepolymer modified urea-formaldehyde resin and preparation method thereof Download PDFInfo
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- CN110615880A CN110615880A CN201910912048.2A CN201910912048A CN110615880A CN 110615880 A CN110615880 A CN 110615880A CN 201910912048 A CN201910912048 A CN 201910912048A CN 110615880 A CN110615880 A CN 110615880A
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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- C08G12/40—Chemically modified polycondensates
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
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- C09J161/32—Modified amine-aldehyde condensates
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Abstract
The invention discloses an epoxy compound and polyol prepolymer modified urea-formaldehyde resin and a preparation method thereof. The method firstly adopts a very low F/U feed ratio (less than 1.1), and simultaneously reduces the content of free formaldehyde in the resin by adjusting the pH value, the temperature and the time in the reaction process; and then, by introducing an epoxy compound with a long-chain structure and a polyol prepolymer, the flexibility of the adhesive structure is increased by the long chain, the bonding strength of the resin is improved by the epoxy group with multiple functionality, the storage stability of the urea-formaldehyde resin with low molar ratio is improved by adding a small amount of stabilizer, and the water resistance and the bonding strength of the resin are improved by adding the modifier. The urea-formaldehyde resin prepared by the invention has the advantages of low free formaldehyde content, high bonding strength, good water resistance and the like, so thatThe formaldehyde emission of the artificial board prepared by the adhesive reaches E0The grade standard.
Description
Technical Field
The invention relates to epoxy compound and polyol prepolymer modified urea-formaldehyde resin and a preparation method thereof, belonging to adhesives required in the field of wood processing.
Background
With the improvement of the living standard of people in China, the industries such as furniture manufacturing, home decoration, logistics packaging and the like are rapidly developed, so that the demand of the artificial board industry in China is greatly improved. The yield of the artificial board in China is rapidly increased by about 30% in year from 2009 to 2011, and in 2016, the first breakthrough of 3 hundred million m is made3Total yield of artificial board 29909 km in the last year3The growth rate is 1.43 percent compared with 2017. The amount of adhesive used to produce these boards exceeds 3000 ten thousand tons.
The urea-formaldehyde resin has the advantages of good bonding strength, quick curing, light color and the like, accounts for more than 80 percent of the glue consumption of the artificial board, particularly has low cost less than 2000 yuan/ton, and is difficult to replace by other resins. However, the urea-formaldehyde resin is easy to release formaldehyde after being used and cured, stimulates nasal mucosa and upper respiratory tract, is a great cause of leukemia and cancer, and seriously harms the health of people. China has set up mandatory national standards of limit of formaldehyde emission in artificial boards and artificial board materials for interior decoration and finishing in 2001 (GB 18580-2001), and stipulates E1Stage E2Standard of artificial board grade, and increase E in 20040Grade standard (the formaldehyde emission of the plate measured by a dryer method is less than or equal to 0.5 mg/L). Although the corresponding regulatory standards are established, the formaldehyde emission of most of the panels on the market is still high due to cost reasons. Therefore, the development of the environment-friendly urea-formaldehyde resin with low cost, excellent bonding performance and low formaldehyde release is beneficial to the technical popularization of the industry.
The most effective method for reducing the formaldehyde emission of the urea-formaldehyde resin adhesive is to reduce the addition of formaldehyde, and the content of free formaldehyde in the resin is reduced along with the reduction of the feeding ratio of formaldehyde to urea, but a series of performance problems are caused. The adhesive has a low cohesive strength, poor stability, low water resistance, and the like. Therefore, the temperature of the molten metal is controlled,the problem to be solved is how to ensure the comprehensive physical properties of the resin while reducing the formaldehyde emission. The traditional modification methods such as the adoption of melamine, phenol, polyvinyl alcohol and the like have difficulty in releasing E formaldehyde due to the problems of molecular structure and active groups0And the performance of the resin such as the bonding strength, the water resistance and the like is ensured under the condition of grade. Therefore, from the structural design of the modifier, the epoxy compound and the long-chain polyol prepolymer of which the main chain is a long flexible chain and the end group is provided with a plurality of epoxy groups are prepared, the long chain increases the flexibility of the adhesive structure, and the epoxy group with multiple functionality improves the bonding strength of the resin, so that the environment-friendly urea-formaldehyde resin adhesive is prepared.
Disclosure of Invention
In view of the above, the present invention provides a urea-formaldehyde resin modified by epoxy compound and polyol prepolymer and a preparation method thereof, wherein the urea-formaldehyde resin is prepared by reacting urea, formaldehyde, epoxy compound, long-chain polyol prepolymer, stabilizer and modifier according to a weak base-weak acid-weak base route. The method firstly adopts a very low F/U feed ratio (less than 1.1), and simultaneously reduces the content of free formaldehyde in the resin by adjusting the pH value, the temperature and the time in the reaction process; and then, by introducing an epoxy compound with a long-chain structure and a long-chain polyol prepolymer, the flexibility of the adhesive structure is increased by the long chain, the bonding strength of the resin is improved by a multifunctional epoxy group, the storage stability of the low-molar-ratio urea-formaldehyde resin is favorably improved by adding a small amount of stabilizer, and the water resistance and the bonding strength of the resin are favorably improved by adding the modifier.
In order to solve the technical problems, the invention provides the following technical scheme:
an epoxy compound and polyol prepolymer modified urea-formaldehyde resin is composed of the following components: 100 parts by weight of urea, 135-148 parts by weight of 37% formaldehyde aqueous solution, 5-20 parts by weight of epoxy compound and long-chain polyol prepolymer, 0.5-1 part by weight of stabilizer, 1-5 parts by weight of modifier, 0.02-0.05 part by weight of acid catalyst and 0.02-0.05 part by weight of alkaline catalyst; the epoxy compound and long-chain polyol prepolymer is prepared by epoxy compound and long-chain polyol under the action of a catalyst for prepolymer preparation.
When the epoxy compound and long-chain polyol prepolymer is prepared from the epoxy compound and polyol prepolymer modified urea-formaldehyde resin, the molar ratio of the epoxy compound to the long-chain polyol is 1: 1, the weight of the added catalyst for preparing the prepolymer is 0.5 percent of that of the epoxy compound, the reaction temperature is 120 ℃, and the reaction time is 2 hours.
The epoxy compound and the polyol prepolymer modified urea-formaldehyde resin are one or more of E44 and E20 in E51.
The epoxy compound and polyol prepolymer modified urea formaldehyde resin has long chain polyol of one or more of polypropylene glycol with polymerization degree of 0-100, polyethylene glycol with polymerization degree of 0-100 and poly-1-4 butanediol with polymerization degree of 0-100.
The catalyst for preparing the prepolymer is one or more of tetrabutylammonium bromide, ethyltriphenylphosphonium bromide and dimethylamine.
The epoxy compound and the polyol prepolymer modified urea resin have one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium abietate and sodium laurate as the stabilizer.
The epoxy compound and the polyol prepolymer are modified to form the urea resin, and the modifier is one or more of melamine, glyoxal and glutaraldehyde.
The epoxy compound and the polyol prepolymer modified urea-formaldehyde resin are prepared by mixing the epoxy compound and the polyol prepolymer modified urea-formaldehyde resin, wherein the acidic catalyst is a formic acid aqueous solution with the mass percentage of 30%.
The epoxy compound and the polyol prepolymer modified urea-formaldehyde resin are prepared by mixing the epoxy compound and the polyol prepolymer modified urea-formaldehyde resin, wherein the alkaline catalyst is a sodium hydroxide aqueous solution with the mass percentage of 20%.
The preparation method of the epoxy compound and polyol prepolymer modified urea resin comprises the following steps:
1) adding 135-148 parts by weight of formaldehyde aqueous solution and 60 parts by weight of urea into the system, controlling the F/U molar ratio of the addition stage to be 1.6-1.8, adding 0.5-1 part by weight of stabilizing agent, and 5-20 parts by weight of epoxy compound and long-chain polyol prepolymer, starting stirring, adjusting the pH value of the system to be 9.0-10.0 by using an alkaline catalyst, heating to 85-95 ℃, and carrying out heat preservation reaction for 30-60 min;
2) adjusting the pH value of the system to 4.0-5.0 by using an acid catalyst, and reacting for 20-40 min;
3) adding 20 parts by weight of urea and 1-5 parts by weight of modifier, and reacting for 30-60 min;
4) cooling to 60-70 ℃, adjusting the pH value of the system to 8.0-9.0, adding 20 parts by weight of urea, keeping the temperature for reaction for 30-60min, cooling and discharging.
In the glue mixing application process of the novel environment-friendly urea-formaldehyde resin, the adhesive is prepared by 100 parts by weight of urea-formaldehyde resin, 10 parts by weight of filler (flour) and 5 parts by weight of curing agent, wherein the curing agent is 10% by mass of ammonium chloride solution, and then the veneer is subjected to gluing and hot pressing to prepare the plywood for detection.
The technical scheme of the invention achieves the following beneficial technical effects:
the urea-formaldehyde resin prepared by the invention has the advantages of low free formaldehyde content, high bonding strength, good water resistance and the like, and the formaldehyde emission of the artificial board prepared by using the adhesive reaches E0The grade standard.
Detailed Description
Example 1
100g of epoxy resin E44 and 88g of polypropylene glycol with the polymerization degree of 0-100 are added into a 500ml four-mouth bottle provided with a reflux condensing device and a stirring device, and the molar ratio is controlled to be 1: 1, adding 0.5g of tetrabutylammonium bromide used as a catalyst for prepolymer preparation, heating to 120 ℃ and reacting for 2 hours to obtain an epoxy compound and long-chain polyol prepolymer.
Adding 148g of formaldehyde aqueous solution, 60g of urea and 0.5g of stabilizer sodium dodecyl benzene sulfonate into a 500ml four-mouth bottle provided with a reflux condensing device and a stirring device, then adding 5g of the epoxy compound and long-chain polyol prepolymer, starting the stirring device, dropwise adding an alkaline catalyst to adjust the pH value of the system to 9.0, and simultaneously starting heating; when the temperature is raised to 85 ℃, keeping the temperature and reacting for half an hour; adjusting the pH value of the system to 5.0 by using an acid catalyst, and reacting for 20 min; adding 20g of urea and 1g of modifier melamine, and reacting for 30 min; and cooling to 70 ℃, adjusting the pH value of the system to 8.0, adding 20 parts by weight of urea, carrying out heat preservation reaction for 30min, cooling and discharging to obtain the urea-formaldehyde resin adhesive. The specific properties of the resin are shown in Table 1.
Example 2
In this embodiment, the epoxy resin E44 was changed to the epoxy resin E51 in the preparation of the epoxy compound and long-chain polyol prepolymer, and the other steps were the same as in example 1.
Example 3
In this embodiment, the epoxy resin E44 was changed to the epoxy resin E20 in the preparation of the epoxy compound and long-chain polyol prepolymer, and the other steps were the same as in example 1.
Example 4
In this embodiment, the procedure of preparing an epoxy compound and a long-chain polyol prepolymer was carried out in the same manner as in example 1 except that polypropylene glycol having a polymerization degree of 0 to 100 was changed to polyethylene glycol having a polymerization degree of 0 to 100 in an equimolar amount.
Example 5
In this embodiment, the procedure of preparing an epoxy compound and a long chain polyol prepolymer was carried out in the same manner as in example 1 except that polypropylene glycol having a polymerization degree of 0 to 100 was changed to poly-1-4-butanediol having a polymerization degree of 0 to 100 in an equimolar amount.
Example 6
In the preparation process of the epoxy compound and long-chain polyol prepolymer, polypropylene glycol with the polymerization degree of 0-100 is changed into polypropylene glycol with the polymerization degree of 0-100 and poly 1-4 butanediol with the polymerization degree of 0-100 in an equimolar number, wherein the molar ratio of the polypropylene glycol to the poly 1-4 butanediol is 1: 1, the other points are the same as in example 1.
Example 7
In the preparation process of the epoxy compound and long-chain polyol prepolymer, polypropylene glycol with the polymerization degree of 0-100 is changed into polyethylene glycol with the polymerization degree of 0-100 and poly 1-4 butanediol with the polymerization degree of 0-100 with equal molar number, wherein the molar ratio of the polyethylene glycol to the poly 1-4 butanediol is 1: 1, the other points are the same as in example 1.
Example 8
In this embodiment, in the process of producing an epoxy compound and a long-chain polyol prepolymer, 0.5g of tetrabutylammonium bromide for prepolymer production was changed to 0.5g of ethyltriphenylphosphonium bromide as a prepolymer production catalyst, and the other steps were the same as in example 1.
Example 9
In this embodiment, in the production of an epoxy compound and a long-chain polyol prepolymer, 0.5g of tetrabutylammonium bromide as a prepolymer production catalyst was changed to 0.5g of dimethylamine as a prepolymer production catalyst, and the other steps were the same as in example 1.
Example 10
In this embodiment, in the production of an epoxy compound and a long-chain polyol prepolymer, 0.5g of tetrabutylammonium bromide as a prepolymer production catalyst was changed to 0.25g of ethyltriphenylphosphonium bromide and 0.25g of dimethylamine as prepolymer production catalysts, and the other steps were the same as in example 1.
Example 11
In this embodiment, the temperature of the epoxy compound and the long chain polyol prepolymer was raised to 130 ℃ instead of 120 ℃ in the preparation process, and the other steps were the same as in example 1.
Example 12
In this embodiment, the temperature of 120 ℃ in the process of producing the epoxy compound and the long chain polyol prepolymer was changed to 150 ℃, and the other steps were the same as in example 1.
Example 13
In this embodiment, the reaction time 2h was changed to 3h in the preparation of the epoxy compound and the long-chain polyol prepolymer, and the other steps were the same as in example 1.
Example 14
In this embodiment, the reaction time 2h was changed to 4h in the preparation of the epoxy compound and the long-chain polyol prepolymer, and the other steps were the same as in example 1.
Example 15
In this embodiment, 148g of the aqueous formaldehyde solution was changed to 135g in the preparation of the epoxy compound and the polyol prepolymer-modified urea resin, and the other steps were the same as in example 1.
Example 16
In this embodiment, 148g of the aqueous formaldehyde solution was changed to 141g in the preparation of the epoxy compound and the polyol prepolymer-modified urea resin, and the other steps were the same as in example 1.
Example 17
In this embodiment, in the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, 0.5g of sodium dodecylbenzenesulfonate as a stabilizer was changed to 0.75g of sodium dodecylbenzenesulfonate, and the rest is the same as in example 1.
Example 18
In this embodiment, in the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, 0.5g of sodium dodecylbenzenesulfonate as a stabilizer is changed to 1.0g of sodium dodecylbenzenesulfonate, and the rest is the same as in example 1.
Example 19
In this embodiment, in the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, 0.5g of sodium dodecylbenzenesulfonate as a stabilizer was changed to 0.5g of sodium dodecylsulfate, and the rest was the same as in example 1.
Example 20
In this embodiment, in the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, 0.5g of sodium dodecylbenzenesulfonate as a stabilizer was changed to 0.5g of sodium dodecylsulfate and 0.5g of sodium abietate, and the other steps were the same as in example 1.
Example 21
In this embodiment, in the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, 0.5g of sodium dodecylbenzenesulfonate as a stabilizer is changed to 0.5g of sodium dodecylsulfate and 0.5g of sodium laurate, and the other steps are the same as those in example 1.
Example 22
In this embodiment, 5g of the epoxy compound and long-chain polyol prepolymer was changed to 10g of the epoxy compound and long-chain polyol prepolymer in the preparation of the epoxy compound and polyol prepolymer modified urea resin, and the other steps were the same as in example 1.
Example 23
In this embodiment, in the preparation of the epoxy compound and polyol prepolymer modified urea resin, 5g of the epoxy compound and long-chain polyol prepolymer was changed to 15g of the epoxy compound and long-chain polyol prepolymer, and the other steps were the same as in example 1.
Example 24
In this embodiment, in the preparation of the epoxy compound and polyol prepolymer modified urea resin, 5g of the epoxy compound and long-chain polyol prepolymer was changed to 20g of the epoxy compound and long-chain polyol prepolymer, and the other steps were the same as in example 1.
Example 25
In this embodiment, the same procedure as in example 1 was repeated except that in the preparation of the epoxy compound and the polyol prepolymer-modified urea resin, the pH of the alkaline catalyst system was changed to 9.0 and 9.5, respectively.
Example 26
In this embodiment, the same procedure as in example 1 was repeated except that in the preparation of the epoxy compound and the polyol prepolymer-modified urea resin, the pH of the alkaline catalyst system was changed to 9.0 and 10, respectively.
Example 27
In this embodiment, the temperature is increased to 85 ℃ instead of 90 ℃ in the preparation of the epoxy compound and the polyol prepolymer modified urea resin, and the other steps are the same as in example 1.
Example 28
In this embodiment, the temperature is increased to 85 ℃ instead of 95 ℃ in the preparation of the epoxy compound and the polyol prepolymer modified urea resin, and the other steps are the same as in example 1.
Example 29
In the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, the temperature is maintained for 30min instead of 45min after the alkaline catalyst is added, and the rest is the same as that in the example 1.
Example 30
In the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, the temperature is maintained for 30min instead of 60min after the alkaline catalyst is added, and the rest is the same as that in the example 1.
Example 31
In this embodiment, the same procedure as in example 1 was repeated except that in the preparation of the epoxy compound and the polyol prepolymer-modified urea resin, the pH of the acidic catalyst system was changed to 5.0 and 4, respectively.
Example 32
In this embodiment, the same procedure as in example 1 was repeated except that the pH of the acidic catalyst was adjusted to 5.0 and the pH of the acidic catalyst was adjusted to 4.5 in the production process of the epoxy compound and the urea resin modified with the polyol prepolymer.
Example 33
In the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, the acidic catalyst is added for reaction for 20min, and the reaction is maintained for 30min, and the rest is the same as that in the example 1.
Example 34
In the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, the acidic catalyst is added for reaction for 20min, and the reaction is maintained for 40min, and the rest is the same as that in the example 1.
Example 35
In the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, 1g of the modifier melamine is added, and the reaction time is changed from 30min to 45min, which is the same as that of example 1.
Example 36
In the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, 1g of the modifier melamine is added, and the reaction time is changed from 30min to 60min, which is the same as that of example 1.
Example 37
In the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, the temperature is reduced to 70 ℃ and then reduced to 60 ℃, and the rest is the same as that in the example 1.
Example 38
In the preparation process of the epoxy compound and the urea resin modified by the polyol prepolymer, the temperature is reduced to 70 ℃ instead of 65 ℃, and the rest is the same as that in the example 1.
Example 39
In this embodiment, the same procedure as in example 1 was repeated except that the pH of the epoxy compound and the polyol prepolymer-modified urea resin was changed to 8.5 instead of 8.0.
Example 40
In this embodiment, the same procedure as in example 1 was repeated except that in the preparation of the epoxy compound and the polyol prepolymer-modified urea resin, the pH of the system was changed to 8.0 and 9, respectively.
EXAMPLE 41
In the preparation process of the epoxy compound and the polyol prepolymer modified urea-formaldehyde resin, 20 parts by weight of urea is added, the heat preservation reaction is carried out for 30min, 20 parts by weight of urea is added, and the heat preservation reaction is carried out for 45min, wherein the rest is the same as that of the embodiment 1.
Example 42
In the preparation process of the epoxy compound and the polyol prepolymer modified urea-formaldehyde resin, 20 parts by weight of urea is added, the heat preservation reaction is carried out for 30min, 20 parts by weight of urea is added, and the heat preservation reaction is carried out for 60min, wherein the rest is the same as that of the embodiment 1.
Example 43
In this embodiment, 1g of the modifier melamine was changed to 3g of melamine in the preparation of the epoxy compound and polyol prepolymer modified urea resin, and the other steps were the same as in example 1.
Example 44
In this embodiment, 1g of the modifier melamine was changed to 5g of melamine in the preparation of the epoxy compound and polyol prepolymer modified urea resin, and the other steps were the same as in example 1.
Example 45
In this embodiment, 1g of the modifier melamine was changed to 1g of glyoxal in the preparation of the epoxy compound and polyol prepolymer modified urea resin, and the rest was the same as in example 1.
Example 46
In this embodiment, 1g of the modifier melamine was changed to 5g of glyoxal in the preparation of the epoxy compound and polyol prepolymer modified urea resin, and the rest was the same as in example 1.
Example 47
In this embodiment, 1g of the modifier melamine was changed to 1g of glutaraldehyde in the preparation of the epoxy compound and polyol prepolymer modified urea resin, and the other steps were the same as in example 1.
Example 48
In this embodiment, 1g of the modifier melamine was changed to 5g of glutaraldehyde in the preparation of the epoxy compound and polyol prepolymer modified urea resin, and the other steps were the same as in example 1.
Example 49
In this embodiment, 1g of the modifier melamine was changed to 1g of melamine and 1g of glutaraldehyde in the preparation of the epoxy compound and polyol prepolymer modified urea resin, and the rest was the same as in example 1.
Example 50
In this embodiment, 1g of the modifier melamine was changed to 1g of melamine and 1g of glyoxal in the preparation of the epoxy compound and polyol prepolymer-modified urea resin, and the rest was the same as in example 1.
Comparative example 1
This comparative example did not incorporate an epoxy compound with a long chain polyol prepolymer, and the rest was the same as in example 1.
Attached: the storage stability period of all the examples and the comparative examples is determined according to GB/T14074-2017, the bonding strength of the plate is determined after the plate is prepared into a sample bar according to the specification in GB/T9846-2012015 and is soaked in hot water at 63 ℃ for 3 hours, and the formaldehyde emission of the plate is determined according to the 24-hour dryer method in GB/T17657-2013.
Table 1 comparison of the properties of the examples
TABLE 2 comparison of formaldehyde emission at different time intervals in the examples
Claims (10)
1. An epoxy compound and polyol prepolymer modified urea-formaldehyde resin is characterized by comprising the following components: 100 parts by weight of urea, 135-148 parts by weight of 37% formaldehyde aqueous solution, 5-20 parts by weight of epoxy compound and long-chain polyol prepolymer, 0.5-1 part by weight of stabilizer, 1-5 parts by weight of modifier, 0.02-0.05 part by weight of acid catalyst and 0.02-0.05 part by weight of alkaline catalyst; the epoxy compound and long-chain polyol prepolymer is prepared by epoxy compound and long-chain polyol under the action of a catalyst for prepolymer preparation.
2. The epoxy compound and polyol prepolymer modified urea-formaldehyde resin according to claim 1, wherein the epoxy compound and long-chain polyol prepolymer is prepared in a molar ratio of epoxy compound to long-chain polyol of 1: 1, the weight of the added catalyst for preparing the prepolymer is 0.5 percent of that of the epoxy compound, the reaction temperature is 120 ℃, and the reaction time is 2 hours.
3. The epoxy compound and polyol prepolymer modified urea-formaldehyde resin as claimed in claim 2, wherein the epoxy resin is one or more of E44 and E20 of E51.
4. The epoxy compound and polyol prepolymer modified urea-formaldehyde resin as claimed in claim 2, wherein the long-chain polyol is one or more of polypropylene glycol having a degree of polymerization of 0 to 100, polyethylene glycol having a degree of polymerization of 0 to 100, and poly-1-4-butylene glycol having a degree of polymerization of 0 to 100.
5. The epoxy compound and polyol prepolymer modified urea-formaldehyde resin according to claim 2, wherein the prepolymer preparation catalyst is one or more of tetrabutylammonium bromide, ethyltriphenylphosphonium bromide and dimethylamine.
6. The epoxy compound and polyol prepolymer modified urea-formaldehyde resin as claimed in claim 1, wherein the stabilizer is one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium abietate and sodium laurate.
7. The epoxy and polyol prepolymer modified urea-formaldehyde resin according to claim 1, wherein the modifier is one or more of melamine, glyoxal, and glutaraldehyde.
8. The epoxy compound and polyol prepolymer modified urea-formaldehyde resin as claimed in claim 1, wherein the acidic catalyst is 30% by mass aqueous formic acid solution.
9. The epoxy compound and polyol prepolymer modified urea-formaldehyde resin as claimed in claim 1, wherein the alkaline catalyst is 20% by mass aqueous sodium hydroxide solution.
10. The method for preparing the epoxy compound and polyol prepolymer modified urea resin according to any one of claims 1 to 9, characterized by comprising the steps of:
1) adding 135-148 parts by weight of formaldehyde aqueous solution and 60 parts by weight of urea into the system, controlling the F/U molar ratio of the addition stage to be 1.6-1.8, adding 0.5-1 part by weight of stabilizing agent, and 5-20 parts by weight of epoxy compound and long-chain polyol prepolymer, starting stirring, adjusting the pH value of the system to be 9.0-10.0 by using an alkaline catalyst, heating to 85-95 ℃, and carrying out heat preservation reaction for 30-60 min;
2) adjusting the pH value of the system to 4.0-5.0 by using an acid catalyst, and reacting for 20-40 min;
3) adding 20 parts by weight of urea and 1-5 parts by weight of modifier, and reacting for 30-60 min;
4) cooling to 60-70 ℃, adjusting the pH value of the system to 8.0-9.0, adding 20 parts by weight of urea, keeping the temperature for reaction for 30-60min, cooling and discharging.
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| CN113224459A (en) * | 2020-01-19 | 2021-08-06 | 厦门大学 | Urea-formaldehyde resin modified ceramic diaphragm and preparation method and application thereof |
| CN113695512A (en) * | 2021-08-31 | 2021-11-26 | 江西特欣实业有限公司 | Preparation method of fast-curing low-temperature collapsible precoated sand |
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| CN113224459A (en) * | 2020-01-19 | 2021-08-06 | 厦门大学 | Urea-formaldehyde resin modified ceramic diaphragm and preparation method and application thereof |
| CN113695512A (en) * | 2021-08-31 | 2021-11-26 | 江西特欣实业有限公司 | Preparation method of fast-curing low-temperature collapsible precoated sand |
| CN113695512B (en) * | 2021-08-31 | 2022-12-02 | 江西特欣实业有限公司 | Preparation method of fast-curing low-temperature collapsible precoated sand |
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