CN101624436B - Environment-protective urea-formaldehyde resin with novel structure as well as preparation method and application thereof - Google Patents
Environment-protective urea-formaldehyde resin with novel structure as well as preparation method and application thereof Download PDFInfo
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- CN101624436B CN101624436B CN2009100890799A CN200910089079A CN101624436B CN 101624436 B CN101624436 B CN 101624436B CN 2009100890799 A CN2009100890799 A CN 2009100890799A CN 200910089079 A CN200910089079 A CN 200910089079A CN 101624436 B CN101624436 B CN 101624436B
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Abstract
The invention discloses an environment-protective urea-formaldehyde resin with novel structure as well as a preparation method and an application thereof. The environment-protective urea-formaldehyde resin with novel structure is prepared from formaldehyde, carbamide, performed polymer of the carbamide and dialdehyde and one or more modifying agents according to the process steps of weak base, weak acid and weak base. In the method, the performed polymer of the carbamide and dialdehyde is introduced in the reaction of matrix resin to prepare resin and generate stable alkyl ether structure (-CH2n-O-CH2n-) so as to reduce the content of methylene ether link in the resin, and meanwhile, the introduction of polyfunctional radicals enhances the degree of crosslinking of the resin, therefore, on the premise of ensuring the cementation strength and the water resistance of the resin, the formaldehyde emission of sheet materials in use is greatly reduced. The urea-formaldehyde resin prepared by the method has the advantages of low free formaldehyde content, low cost, simple process and favorable cementation strength. The formaldehyde emission of sheet materials manufactured by the sizing agent reaches the standard of E0 grade.
Description
Technical field
The present invention relates to a kind of preparation method and application of novel texture environment-friendly urea-formaldehyde resin, the tackiness agent that makes is applied to wood working industry especially.
Background technology
About 9,409 ten thousand m of China's wood-based plate output in 2008
3, risen to the first wood-based plate big producing country in the world, also become wood adhesive, particularly urea-formaldehyde resin adhesive the first in the world big producing country, Wood-based Panel Production uses urea-formaldehyde resin tamanori (dried glue meter) more than 4,000,000 tons/year.The export volume of 08 year China's wood-based plate is 7,170,000 m
3, than descending nearly 18.36% 07 year same period.This mainly is because the more and more national environmental consciousness constantly strengthens, environmental protection standard progressively improves, they begin the harmful chemical burst size of Wood products such as wood-based plate is strict with, and especially the burst size of formaldehyde is subjected to the attention of foreign market especially.The raising of these target levels of product quality makes domestic Wood-based Panel Production enterprise be faced with more test.
Urea-formaldehyde resin because have that production cost is low, advantage such as sufficient raw, bonding property are good, quick solidifying and glue-line are colourless, in wood-based panel industry, obtained using widely, account for more than 80% of wood-based plate glue consumption, become the kind of consumption maximum in the present tackiness agent, especially its cheap price is that other tackiness agent can't replace.Yet urea-formaldehyde resin can constantly discharge formaldehyde in production and use, environment is caused severe contamination.Because glued board, core-board, shaving board, medium density fibre board (MDF) with the urea-formaldehyde resin adhesive manufacturing are mainly used in furniture manufacturing and interior decoration, meeting serious harm people's is healthy.Along with the raising of living standards of the people and the enhancing and the enforcement of environmental regulation both at home and abroad of environmental consciousness, the environment friendly artificial board that uses low formaldehyde to discharge has become inexorable trend.China has just formulated " burst size of methanal is limited the quantity of in indoor decorating material---wood-based plate and the goods thereof " mandatory national standard (GB18580-2001) in calendar year 2001, has stipulated E
1Level, E
2Level wood-based plate standard.This means and only produce the urea-formaldehyde resin adhesive that meets " environmental protection, nuisanceless ", could satisfy the demand of domestic and international market.
Existing modified urea-formaldehyde resin adhesive, it mainly is the burst size that reduces formaldehyde by content that reduces free formaldehyde in the resin and methods such as adding formaldehyde-trapping agent, but because the ageing problem of formaldehyde-trapping agent can not fundamentally solve the problem that formaldehyde discharges.This is because have unstable structures such as methylene ether link and methylol key in the urea-formaldehyde resin, and reversible reaction takes place easily, discharges formaldehyde thereby decompose, this process is persistent very long, and with the same life-span of urea-formaldehyde resin, that is to say, just have formaldehyde to discharge as long as use the urea-formaldehyde resin wood-based plate.Fundamentally change unstable structure such as existing methylene ether link and methylol in the urea-formaldehyde resin, be only the termination method that formaldehyde discharges in the urea-formaldehyde resin that solves.In currently used various modified additive and the method, the use of dialdehyde is mainly used to improve the physical and mechanical properties and the water tolerance thereof of urea-formaldehyde resin.As far back as 1978, William etc. just were configured to the aqueous solution as the linking agent in the urea-formaldehyde resin foaming process with oxalic dialdehyde with oxalic acid, phosphoric acid etc., were used for improving the mechanical strength of urea aldehyde insulation bubble.WO94/04584 adopts dialdehyde and formaldehyde, urea and aminated compounds to react under acidic conditions, the ring urea structure that generates has improved the physical and mechanical properties of resin, but this resin free formaldehyde content is higher, and about 0.2%, and prepared sheet material burst size of methanal can only reach E
1Grade standard, the unstable structure of long-term release formaldehyde still is present among the sheet material in a large number.So, need find out new method and obtain low burst size of methanal, the resin that bonding capacity is good.
Summary of the invention
The invention provides a kind of preparation method and application of novel texture environment-friendly urea-formaldehyde resin, adopt weak base-weak acid-weakly alkaline synthesis route,, make resin generate stable alkyl oxide ((CH by introducing the performed polymer of urea and dialdehyde
2)
n-O-(CH
2)
n-) structure, the tackiness agent that makes removes in use that burst size of methanal reaches E
0Outside the grade standard, guarantee consolidation strength and excellent water tolerance simultaneously.
Synthetic novel texture environment-friendly urea-formaldehyde resin glue of the present invention, made according to following proportioning by performed polymer, properties-correcting agent, basic catalyst and an acidic catalyst of urea, formaldehyde, urea and dialdehyde: urea 122 weight parts, mass percent are 35% formalin: the performed polymer of 172-197 weight part, dialdehyde and urea: 10-100 weight part, properties-correcting agent: 0.05-5 weight part, an acidic catalyst: 0.02-0.05 weight part, basic catalyst: 0.02-0.05 weight part; The mol ratio of formaldehyde and urea is 1.0-1.2; Described basic catalyst is an alkali aqueous solution, and an acidic catalyst is an aqueous acid.
The mol ratio of dialdehyde and urea is 0.5-2.0 in the performed polymer of dialdehyde and urea, the synthetic method of this performed polymer is as follows: having under the state of stirring, dialdehyde and urea are added reactor, regulate the pH value to 3.0-5.0 with aqueous acid, be warming up to 50-80 ℃, temperature rise rate is at 1.0-3.0 ℃/min, the discharging of insulation reaction 20-40min postcooling.
Dialdehyde be oxalic dialdehyde, mda, glutaraldehyde, hexanedial, heptan one of dialdehyde, suberic aldehyde, two or more mixing by any ratio.
Aqueous acid is one of aqueous formic acid, aqueous sulfuric acid, aqueous hydrochloric acid.
Alkali aqueous solution is one of aqueous sodium hydroxide solution, the trolamine aqueous solution, vulkacit H aqueous solution.
Properties-correcting agent is one of trimeric cyanamide, polyvinyl alcohol, TriMethylolPropane(TMP), glycerol, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose.
The preparation method of modified environment protection type urea formaldehyde resin of the present invention, step is as follows:
1) having under the state of stirring,, regulating pH value to 9.0, be warming up to 90 ℃, insulation reaction 50min with alkali aqueous solution with formalin, the urea 75 weight parts adding reactor of 172-197 weight part mass percent 35%;
2) with aqueous acid regulation system pH value to 4.8, add urea 20 weight parts, reaction 20min;
3) be cooled to 70 ℃, regulate pH value to 7.2, add urea 17 weight parts with alkali aqueous solution;
4) be warming up to 80 ℃, with adding properties-correcting agent 0.5-5 weight part and urea 10 weight parts, insulation reaction 30min;
5) be cooled to 40 ℃, add alkali aqueous solution regulation system pH value to 8.0, cooling discharging obtains urea-formaldehyde resin;
Urea and dialdehyde performed polymer 10-100 weight part are in above-mentioned preparation method's step 1), step 2) or during step 3) the disposable and urea of three phases add simultaneously.
The application of novel texture environment-friendly urea-formaldehyde resin of the present invention in tackiness agent, described tackiness agent is made by the urea-formaldehyde resin of 100 weight parts, the filler of 15 weight parts, the solidifying agent of 5 weight parts.Its solidifying agent be ammonium chloride, ammonium persulphate, Secondary ammonium phosphate, ammonium phosphate, urea with the performed polymer of dialdehyde in a kind of, two or more mixes by any ratio.
The environment-friendly urea-formaldehyde resin of the present invention preparation after testing, free formaldehyde content is less than 0.1%, the glued board burst size of methanal that makes thus reaches E
0Grade standard, not yellowing of glue-line, sheet material behind the hot cooking intensity greater than 0.8MPa.The preparation method has technology advantage simple, with low cost.
Description of drawings
Fig. 1 embodiment 1 and Comparative Examples 1 infrared comparison diagram A (wave number 3200cm
-1-2700cm
-1)
Fig. 2 embodiment 1 and Comparative Examples 1 infrared comparison diagram B (wave number 1800cm
-1-1400cm
-1)
Fig. 3 embodiment 1 and Comparative Examples 1 infrared comparison diagram C (wave number 1400cm
-1-1000cm-
-1)
(the common urea-formaldehyde resin of UF-wherein; UFGU-urea and glutaraldehyde performed polymer modified urea-formaldehyde resin).
Embodiment
Embodiment 1
The performed polymer (GU) for preparing urea and glutaraldehyde earlier is stand-by: in the 500ml four-hole bottle of reflux condensate device and whipping appts is housed, the glutaraldehyde water solution 240g that adds mass percent 50%, urea 48.04g, with aqueous formic acid regulation system pH=4.0, begin heating simultaneously, temperature rise rate is 2.0 ℃/min; Treat that temperature rises to 65 ℃, be cooled to room temperature behind the insulation reaction 30min, discharging obtains the performed polymer (GU) of urea and glutaraldehyde.The mol ratio of this system glutaraldehyde and urea is 1.5: 1.
In another 500ml four-hole bottle, open reflux condensate device and whipping appts, add the formalin 197.34g of mass percent 35%, urea 75.00g, dropping sodium aqueous solution regulation system pH=9.0 begins heating simultaneously; Treat that temperature rises to 90 ℃, insulation reaction 50min; With aqueous formic acid regulation system pH=4.8, add urea 20.00g, reaction 20min; Be cooled to 70 ℃,, add performed polymer (GU) 40.00g of 17.00g urea and urea and glutaraldehyde with aqueous sodium hydroxide solution regulation system pH=7.2; Be warming up to 80 ℃, add trimeric cyanamide 0.5g and residue urea 10.00g, insulation reaction 30min; Be cooled to 40 ℃, add aqueous sodium hydroxide solution regulation system pH=8.0, cooling discharging obtains urea-formaldehyde resin adhesive.Total mol ratio of this system formaldehyde and urea is 1.15: 1, and addition stage at initial stage control formaldehyde and urea mol ratio are 1.8: 1, and the ratio that each stage urea adds quality is 75: 20: 17: 10.This urea-formaldehyde resin is in application, and described tackiness agent is made by 20% (mass percentage concentration) ammonium chloride of the urea-formaldehyde resin of 100 weight parts, the filler of 15 weight parts (flour or starch), 5 weight parts.
Embodiment 2
Holding temperature is 50 ℃ among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 3
Holding temperature is 60 ℃ among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 4
Holding temperature is 70 ℃ among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 5
Holding temperature is 80 ℃ among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 6
Temperature rise rate is 1.0 ℃/min among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 7
Temperature rise rate is 1.5 ℃/min among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 8
Temperature rise rate is 2.5 ℃/min among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 9
Temperature rise rate is 3.0 ℃/min among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 10
Strong acid aqueous solution is an aqueous sulfuric acid among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 11
Strong acid aqueous solution is an aqueous hydrochloric acid among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 12
The pH value is 3.0 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 13
The pH value is 5.0 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 14
The mol ratio of glutaraldehyde and urea is 0.5 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 15
The mol ratio of glutaraldehyde and urea is 1.0 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 16
The mol ratio of glutaraldehyde and urea is 1.2 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 17
The mol ratio of glutaraldehyde and urea is 1.4 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 18
The mol ratio of glutaraldehyde and urea is 1.6 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 19
The mol ratio of glutaraldehyde and urea is 1.8 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 20
The mol ratio of glutaraldehyde and urea is 2.0 among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 21
The time of insulation reaction is 20min among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 22
The time of insulation reaction is 40min among the preparation method of the performed polymer of present embodiment urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 23
Present embodiment adds the performed polymer 10g modification of urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 24
Present embodiment adds the performed polymer 30g modification of urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 25
Present embodiment adds the performed polymer 50g modification of urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 26
Present embodiment adds the performed polymer 70g modification of urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 27
Present embodiment adds the performed polymer 100g modification of urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 28
Present embodiment is in the performed polymer 40g modification of step 1) adding urea and glutaraldehyde, and other are identical with embodiment 1.
Embodiment 29
Present embodiment is in step 2) add the performed polymer 40g modification of urea and glutaraldehyde, other are identical with embodiment 1.
Embodiment 30
Present embodiment adopt urea and oxalic dialdehyde performed polymer resin is carried out modification, add-on is 40g, because glyoxal solution has strongly-acid, need use strong alkali aqueous solution regulation system pH=4.0 when preparing performed polymer, other are identical with embodiment 1.Urea and oxalic dialdehyde performed polymer viscosity big, the urea-formaldehyde resin degree of crosslinking that obtains, its shelf stable for periods is shorter than embodiment 1.
Embodiment 31
Present embodiment adopts the performed polymer of urea and mda that resin is carried out modification, and add-on is 40g, and other are identical with embodiment 1.
Embodiment 32
Present embodiment adopts the performed polymer of urea and hexanedial that resin is carried out modification, and add-on is 40g, and other are identical with embodiment 1.Owing to introduced longer segment, improved the compliance of resin, the sheet material consolidation strength that obtains is better.
Embodiment 33
Present embodiment adopt urea and heptan dialdehyde performed polymer resin is carried out modification, add-on is 40g, other are identical with embodiment 1.
Embodiment 34
Present embodiment adopts the performed polymer of urea and suberic aldehyde that resin is carried out modification, and add-on is 40g, and other are identical with embodiment 1.Because reactivity ratio's glutaraldehyde of suberic aldehyde is low, boiling point is 140 ℃, need improve processing temperature during pressed sheet.
Embodiment 35
Present embodiment adopts the performed polymer of urea and dialdehyde (oxalic dialdehyde and glutaraldehyde mol ratio 1: 1) that resin is carried out modification, and add-on is 40g, and other are identical with embodiment 1.
Embodiment 36
Present embodiment adopts the performed polymer of urea and dialdehyde (oxalic dialdehyde and suberic aldehyde mol ratio 1: 1) that resin is carried out modification, and add-on is 40g, and other are identical with embodiment 1.
Embodiment 37
Present embodiment adopts the performed polymer of urea and dialdehyde (mol ratio of oxalic dialdehyde and glutaraldehyde, suberic aldehyde 1: 2: 1) that resin is carried out modification, and add-on is 40g, and other are identical with embodiment 1.
Embodiment 38
Present embodiment adds properties-correcting agent trimeric cyanamide 1 weight part in system after the prepolymer reaction that adds urea and dialdehyde, other are identical with embodiment 1.The viscosity of resin increases after the modification, and stability increases.
Embodiment 39
Present embodiment adds properties-correcting agent trimeric cyanamide 3 weight parts in system after the prepolymer reaction that adds urea and dialdehyde, other are identical with embodiment 1.The viscosity of resin increases after the modification, and stability increases.
Embodiment 40
Present embodiment adds properties-correcting agent trimeric cyanamide 5 weight parts in system after the prepolymer reaction that adds urea and dialdehyde, other are identical with embodiment 1.The viscosity of resin increases after the modification, and stability increases.
Embodiment 41
Present embodiment adds properties-correcting agent polyvinyl alcohol 0.5 weight part in system after the prepolymer reaction that adds urea and dialdehyde, other are identical with embodiment 1.The viscosity of resin increases after the modification, and stability increases.
Embodiment 42
Present embodiment adds properties-correcting agent polyvinyl alcohol 1 weight part in system after the prepolymer reaction that adds urea and dialdehyde, other are identical with embodiment 1.The viscosity of resin increases after the modification, and stability increases.
Embodiment 43
The properties-correcting agent that present embodiment adds is TriMethylolPropane(TMP) 0.5 weight part, and other are identical with embodiment 1.The viscosity of resin increases after the modification, and consolidation strength increases.
Embodiment 44
The properties-correcting agent that present embodiment adds is glycerol 0.5 weight part, and other are identical with embodiment 1.The viscosity of resin increases after the modification, and consolidation strength increases.
Embodiment 45
The properties-correcting agent that present embodiment adds is glycerol 1 weight part, and other are identical with embodiment 1.The viscosity of resin increases after the modification, and consolidation strength increases.
Embodiment 46
The properties-correcting agent that present embodiment adds is glycerol 3 weight parts, and other are identical with embodiment 1.The viscosity of resin increases after the modification, and consolidation strength increases.
Embodiment 47
The properties-correcting agent that present embodiment adds is glycerol 5 weight parts, and other are identical with embodiment 1.The viscosity of resin increases after the modification, and consolidation strength increases.
Embodiment 48
The properties-correcting agent that present embodiment adds is Walocel MT 20.000PV 0.5 weight part, and other are identical with embodiment 1.The viscosity of resin increases after the modification, and stability increases.
Embodiment 49
The properties-correcting agent that present embodiment adds is Natvosol 0.5 weight part, and other are identical with embodiment 1.The viscosity of resin increases after the modification, and stability increases.
Embodiment 50
The properties-correcting agent that present embodiment adds is hydroxypropylcellulose 0.5 weight part, and other are identical with embodiment 1.The viscosity of resin increases after the modification, and stability increases.
Embodiment 51
The total mol ratio of present embodiment formaldehyde and urea is 1.1: 1, and addition stage at initial stage control formaldehyde and urea mol ratio are 1.8: 1, and other are identical with embodiment 1.
Embodiment 52
The total mol ratio of present embodiment formaldehyde and urea is 1.05: 1, and addition stage at initial stage control formaldehyde and urea mol ratio are 2.0: 1, and other are identical with embodiment 1.
Embodiment 53
The total mol ratio of present embodiment formaldehyde and urea is 1: 1, and addition stage at initial stage control formaldehyde and urea mol ratio are 2.0: 1, and other are identical with embodiment 1.
Embodiment 54
Present embodiment is in adhesive applications, and described tackiness agent is by the urea-formaldehyde resin of 100 weight parts, the filler of 15 weight parts, the composite curing agent of 5 weight parts: 20% ammonium persulphate and 20% ammonium phosphate weight ratio are made at 2: 3, and other are identical with embodiment 1.
Embodiment 55
Present embodiment is in adhesive applications, described tackiness agent is by the urea-formaldehyde resin of 100 weight parts, the filler of 15 weight parts, the composite curing agent of 5 weight parts: the performed polymer of 20% ammonium sulfate and urea and glutaraldehyde (mol ratio of glutaraldehyde and urea is 1.5) weight ratio is made at 1: 4, and other are identical with embodiment 1.
Embodiment 56
Present embodiment is in adhesive applications, described tackiness agent is by the urea-formaldehyde resin of 100 weight parts, the filler of 15 weight parts, the composite curing agent of 5 weight parts: 20% ammonium persulphate, 20% ammonium phosphate urea and performed polymer (mol ratio of glutaraldehyde and urea the is 1.5) weight ratio of glutaraldehyde are made at 2: 3: 2, and other are identical with embodiment 1.
Comparative Examples 1
Present embodiment does not add the performed polymer of urea and glutaraldehyde, and other are identical with embodiment 1.
Comparative Examples 2
Present embodiment does not add properties-correcting agent, and other are identical with embodiment 1.
Attached: the water resistance test of all embodiment, Comparative Examples is to soak by sheet material being put into 63 ℃ of hot water, and whether observing comes unglued is weighed; The numerical value of consolidation strength is sheet material to be put into 63 ℃ of hot water immersions measure after 3 hours.
Table 1 embodiment 1 urea-formaldehyde resin adhesive performance
| Index name | Unit | Performance | Testing method |
| Outward appearance | Colourless, white or faint yellow inclusion-free uniform liquid | GB/T14074.1-1993 | |
| The pH value | 7.5 | GB/T14074.4-1993 | |
| Solids content | ％ | 58.2 | GB/T14074.5-1993 |
| Free formaldehyde content | ％ | 0.084 | GB/T14074.16-1993 |
| Viscosity | cP | 311 | GB/T14074.3-1993 |
| Storage period | d | ＞30 | GB/T14074.9-1993 |
| Consolidation strength | MPa | (0.94 sheet material soaks in 63 ℃ of hot water after 3 hours and measures) | GB/T9846-2004 |
| Burst size of methanal | mg*L -1 | 0.3 | GB/T17657-1999 |
Table 2 embodiment performance comparison
Table 3 embodiment 1 and Comparative Examples 1 infrared comparison diagram analysis
(the common urea-formaldehyde resin of UF-; UFGU-urea and glutaraldehyde performed polymer modified urea-formaldehyde resin)
| 2950cm -1Left and right sides ether, CH 2OH、 -NCH 2-in symmetrical V CH | 1660-1630cm -1The C=O stretching vibration; The formation vibration of C=O, C-N, NH (flexural vibration) | 1150-1130cm -1 NCH 2The stretching vibration of C-O, C-N in N, the aliphatic ether (in) | ?1060cm -1Left and right sides C-O-C antisymmetric stretching vibration (by force) | |
| The UF curve | 2962.575 | 1639.446 | 1134.111 | 1031.886 |
| The UFGU curve | 2951.002 | 1651.018 | 1129.52 | 1025.89 |
1.2950cm
-1About ether, CH
2OH ,-NCH
2-in symmetrical V
CHMove to the lower, this is because the CO-NH-CHOH (CH that introduces
2)
3The electronic action that pushes away of a large amount of methylene radical causes in-CHO the structure;
2.1660-1630cm
-1About mainly be the C=O stretching vibration peak, because that contain a large amount of most generations in the performed polymer of urea and glutaraldehyde is secondary amine-NH-, compare with the tertiary amine groups-N-of common urea-formaldehyde resin, the electron repulsive ability of secondary amine-NH-is low, thereby makes 1660-1630cm in the resin
-11660cm
-1About the C=O stretching vibration peak hoist mobile;
3. the introducing of urea and glutaraldehyde performed polymer makes to have produced alkyl oxide structure ((CH in the urea-formaldehyde resin
2)
n-O-(CH
2)
n-), the electronic action that pushes away of methylene radical makes 1150-1130cm in this structure
-1The NCH of place
2The stretching vibration of C-O, C-N moves to the lower in N, the aliphatic ether;
4. the introducing of urea and glutaraldehyde performed polymer makes to have produced alkyl oxide structure ((CH in the urea-formaldehyde resin
2)
n-O-(CH
2)
n-), the electronic action that pushes away of methylene radical makes 1060cm in this structure
-1Left and right sides C-O-C antisymmetric stretching vibration moves to the lower.
Claims (3)
1. the preparation method of a urea-formaldehyde resin, this urea-formaldehyde resin comprises performed polymer, properties-correcting agent, basic catalyst and an acidic catalyst of urea, formaldehyde, urea and dialdehyde; Wherein urea 122 weight parts, mass percent are 35% formalin: the performed polymer of 172-197 weight part, dialdehyde and urea: 10-100 weight part, properties-correcting agent: 0.5-5 weight part, an acidic catalyst: 0.02-0.05 weight part, basic catalyst: 0.02-0.05 weight part; The mol ratio of formaldehyde and urea is 1.0-1.15; Described basic catalyst is an alkali aqueous solution, and an acidic catalyst is an aqueous acid:
The mol ratio of dialdehyde and urea is 0.5-2.0 in the performed polymer of described dialdehyde and urea, the synthetic method of this performed polymer is as follows: having under the state of stirring, dialdehyde and urea are added reactor, regulate the pH value to 3.0-5.0 with aqueous acid, be warming up to 50-80 ℃, temperature rise rate is at 1.0-3.0 ℃/min, the discharging of insulation reaction 20-40min postcooling;
It is characterized in that: step is as follows:
1) having under the state of stirring,, regulating pH value to 9.0, be warming up to 90 ℃, insulation reaction 50min with alkali aqueous solution with formalin, the urea 75 weight parts adding reactor of 172-197 weight part mass percent 35%;
2) with aqueous acid regulation system pH value to 4.8, add urea 20 weight parts, reaction 20min;
3) be cooled to 70 ℃, regulate pH value to 7.2, add urea 17 weight parts with alkali aqueous solution;
4) be warming up to 80 ℃, with adding properties-correcting agent 0.5-5 weight part and urea 10 weight parts, insulation reaction 30min;
5) be cooled to 40 ℃, add alkali aqueous solution regulation system pH value to 8.0, cooling discharging obtains urea-formaldehyde resin;
Urea and dialdehyde performed polymer 10-100 weight part are in above-mentioned preparation method's step 1), step 2) or during step 3) the disposable and urea of three phases add simultaneously.
2. according to the application of the urea-formaldehyde resin of the described method of claim 1 preparation, it is characterized in that: urea-formaldehyde resin is applied in the tackiness agent, and described tackiness agent is made by the urea-formaldehyde resin of 100 weight parts, the filler of 15 weight parts, the solidifying agent of 5 weight parts.
3. application according to claim 2 is characterized in that: solidifying agent be ammonium chloride, ammonium persulphate, Secondary ammonium phosphate, ammonium phosphate, urea with the performed polymer of dialdehyde in a kind of, two or more mixes by any ratio.
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|---|---|---|---|
| CN2009100890799A CN101624436B (en) | 2009-08-03 | 2009-08-03 | Environment-protective urea-formaldehyde resin with novel structure as well as preparation method and application thereof |
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| CN102030876B (en) * | 2010-10-12 | 2013-05-01 | 北京化工大学 | New structural urea resin with ultralow formaldehyde release and preparation method thereof |
| CN102229791A (en) * | 2011-06-14 | 2011-11-02 | 王喆 | Environment-friendly type urea-formaldehyde resin adhesive and production method thereof |
| CN102585131B (en) * | 2012-02-21 | 2013-07-24 | 北京化工大学 | Glycidyl ether modified urea formaldehyde resin and preparation method thereof |
| CN103756607B (en) * | 2013-12-20 | 2015-09-16 | 北京林业大学 | Additive of urea-formaldehyde resin adhesive and preparation method thereof and application |
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| US4482699A (en) * | 1983-07-25 | 1984-11-13 | Borden, Inc. | Low emitting aqueous formulations of aminoplast resins and processes for manufacturing them |
| CN101311200A (en) * | 2007-05-25 | 2008-11-26 | 北京化工大学 | Method for preparing post-crosslinking modified urea-formaldehyde resin adhesive |
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