CN1307266C - New type radiation solidified aqueous resin and synthetic method - Google Patents
New type radiation solidified aqueous resin and synthetic method Download PDFInfo
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- CN1307266C CN1307266C CNB2005100314207A CN200510031420A CN1307266C CN 1307266 C CN1307266 C CN 1307266C CN B2005100314207 A CNB2005100314207 A CN B2005100314207A CN 200510031420 A CN200510031420 A CN 200510031420A CN 1307266 C CN1307266 C CN 1307266C
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- acrylamide
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Abstract
The present invention discloses radiation solidified aqueous resin and a synthetic method thereof. The structure of the aqueous resin is disclosed in the specification, wherein the average value of n is from 1.5 to 2.0. The synthetic method of the aqueous resin comprises the following steps: (1) mixing materials have the following ratio: urea to glyoxal to acrylamide is 1 mol: 3 to 4 mol: 1.3 to 2 mol, and the use quality of a polymerization inhibitor is 0.5 mass% of the acrylamide; (2) the synthetic method has the following technological process and conditions: firstly, urea and 40% of glyoxal water solution are put in a reactor, are stirred and are heated to 60 to 65 DEG C; pH values are regulated to 7 to 8 by an alkaline reagent, and the mixture reacts for 2 hours; a sample is fetched, and the content of aldehyde radical is measured; when the content of the aldehyde radical is smaller than 11%, the acrylamide and a polymerization inhibitor are added, and the mixture is continuously heated to 90 to 95DEGC to react for 2 hours; a sample is fetched, and the content of aldehyde radical is measured; when the content of the aldehyde radical is smaller than 2%, reaction is stopped, and the mixture is filtered and discharged. The resin can be diluted with water in any proportions into radiation solidified aqueous paint; after the paint is dried by ultraviolet rays, a coating film has the characteristics of high gloss and toughness; the paint has high adhesiveness to metal, paper and wood and is radiation solidified resin paint with favorable performance.
Description
Technical field
The present invention relates to a kind of new type radiation solidified aqueous resin and synthetic method thereof.
Background technology
The coating developing direction of 21st century is to popularize pollution-free environmental protection coating material in an all-round way.Environmental protection coating material mainly concentrates on three aspects: water-borne coatings, radiation curable coating and water-borne coatings.Existing water-borne coatings is mainly used in building coating, and in the application of other field seldom, and reason is an also defectiveness of the performance of filming; Radiation curable coating can be used for each industrial coating field because of its good film performance, owing to adopt expensive reactive thinner, the cost height is restricted its application.Therefore, the water-borne coatings of developing novel radiation curable seems particularly urgent.This coating can have the premium properties of radiation curable coating with cheap water as thinner.
But existing radiation curable aqueous resin price costliness is generally 80-90 unit/Kg, does not have industrial value.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned the deficiencies in the prior art, provides a kind of cheap, and raw material is easy to get, the new type radiation solidified aqueous resin of excellent property and synthetic method.
For solving the problems of the technologies described above, the present invention adopts following technical proposals.
New type radiation solidified aqueous resin of the present invention has following structural formula:
N mean value is 1.5～2.0
Molecular-weight average is 320-450, range of viscosities 150～250 seconds (4# paint cup), and outward appearance is a yellow transparent, colourity is 150～200APHA.Aldehyde group content is less than 2% (mass ratio), and odorless is tasteless, nontoxic, nonirritant; Contain the end carbon-to-carbon double bond in its structure, can be used for radiation curing; Hydroxy radical content is at 20～25% (mass ratioes), have good water-soluble, the used water infinite dilution.
New type radiation solidified aqueous resin synthetic method of the present invention is:
(1) ratio of components:
Urea: oxalic dialdehyde: acrylamide=1mol: 3～4mol: 1.3～2mol; The stopper consumption is 0.5% of an acrylamide quality.
(2) technological process and condition:
Glyoxal water solution with urea and 40% drops in the reactor earlier, stirring is warming up to 60～65 ℃, transfers pH to 7～8 with alkaline reagents, reacts 2 hours, aldehyde group content is surveyed in sampling, when aldehyde group content during less than 11% (mass ratio), drop into acrylamide and stopper, continue to be warming up to 90～95 ℃ of reactions 2 hours, aldehyde group content is surveyed in sampling, when aldehyde group content during less than 2% (mass ratio), stopped reaction filters discharging.
Used alkaline reagents is: sodium hydroxide or ammonium hydroxide or trolamine or triethylamine.
Used stopper is MEHQ or 2,6 ditertiary butyl p cresol or triphenylphosphine or Resorcinol.
The reaction formula of water-base resin of the present invention is as follows:
Polymerization degree n=1.5～2
Water-base resin used water of the present invention infinite dilution is mixed with aqueous radiation curable coating on request, and nontoxic, nothing is smelt, and is tasteless, non-stimulated.Test shows that the radiation curable coating of preparation can be used for plastics, paper, timber and coating metal surfaces, and film coated surface is plentiful, and mechanical property is good.
This synthetic method is simple, and the reaction conditions gentleness is easy to control, and the no three wastes produce in the production process, are typical process for cleanly preparing.
Specific embodiments
Embodiment 1
In the 1000ml there-necked flask that band stirs, add urea 90g (1.5mol), 40% glyoxal water solution 362.5g, stirring is warming up to 60～65 ℃, and the NaOH aqueous solution with 10% is regulated PH=7～8, reacts two hours, it is 10.5% that aldehyde group content is surveyed in sampling, is cooled to room temperature, filters discharging.Viscosimetric is 160 seconds (25 ℃), and colourity 150 (APHA), hydroxyl value are 22% (mass ratio).
Embodiment 2
In the 1000L stainless steel cauldron, drop into 120kg urea, 40% glyoxal water solution 435kg adds trolamine 6kg, stirs, be warming up to 60～65 ℃, surveying PH is 7.5, reacts 2.5 hours, and it is 10.0% (mass ratio) that aldehyde value is surveyed in sampling, throw 141Kg propionic acid amide and 0.7Kg2, the 6-ditertbutylparacresol.Be warming up to 90-95 ℃, reacted 3 hours, surveying aldehyde value is 1.72% (mass ratio), is cooled to room temperature, filters packing with 300 order filter clothes; Viscosimetric is 170 seconds (20 ℃), and colourity 150 (APHA), hydroxyl value are 21% (mass ratio).
Embodiment 3
Preparation of consolidated floor UV cured primer and application:
| Water-base resin of the present invention | 1000 parts |
| Water | 200 parts |
| Talcum powder | 200 parts |
| Photosensitizers (trade mark 1173) | 20 parts |
| Other auxiliary agent | 10 parts |
Above-mentioned material weighed in proportion places 5 liters of glass cylinderes, disperses 30 minutes with high speed dispersor, and viscosimetric is 120 seconds (4
#Paint cup), outward appearance is the oyster white thick liquid, solid content 60%.By industrial UV-light automatic painting line, roller coat through infrared cup dry (about 30 seconds), obtains even dry coating through ultraviolet curing (about 0.5 second) again on consolidated floor with coatings formulated, and it is as follows to record film performance:
| Adhesive rate (method of scoring) | 100％ |
| Pencil hardness | 1-2H |
| Glossiness (60 ° of input angles) | 80％ |
Detect explanation, this coating has fabulous tack to consolidated floor.
Embodiment 4:
The preparation and the performance test of UV curable water-borne metal cap optical coating:
| Water-base resin of the present invention | 100 parts |
| Water | 30 parts |
| Adhesion promoter | 0.5 part |
| Photosensitizers | 4 parts |
| Photosensitizer additive | 2 parts |
| Other auxiliary agent | 1 part |
Above-mentioned material metage in the beaker of 200ml, is stirred well; Recording viscosity is 25 seconds (25 ℃) solid contents 52%.Be sprayed on the tinplate standard test sample plate, through ultra red ray drying, remove moisture content, through the ultraviolet light polymerization film forming, it is as follows to record film properties again:
| Glossiness (60 ° of input angles) % | 82 |
| Adhesive rate (cross-hatching) % | 100 |
| Pencil hardness | 2H |
| Snappiness (Ф mm) | 0 |
| The ultraviolet light polymerization time | 0.5 second |
Claims (4)
1, a kind of new type radiation solidified water-base resin is characterized in that this water-base resin has following structural formula:
N mean value is 1.5～2.0,
Molecular-weight average is 320-450, and range of viscosities is by 4
#Paint cup is 150～250 seconds, and outward appearance is a yellow transparent, and colourity is 150～200APHA, aldehyde group content by mass ratio less than 2%, odorless, tasteless, nontoxic, nonirritant; Contain the end carbon-to-carbon double bond in its structure, hydroxy radical content by mass ratio 20～25%.
2, a kind of synthetic method of new type radiation solidified water-base resin as claimed in claim 1 is characterized in that comprising following processing condition:
(1) ratio of components:
Urea: oxalic dialdehyde: acrylamide=1mol: 3～4mol: 1.3～2mol; The stopper consumption is 0.5% of an acrylamide quality;
(2) technological process and condition:
Glyoxal water solution with urea and 40% drops in the reactor earlier, stirring is warming up to 60～65 ℃, transfers pH to 7～8 with alkaline reagents, reacts 2 hours, aldehyde group content is surveyed in sampling, when aldehyde group content less than 11% the time, drop into acrylamide and stopper, continue to be warming up to 90～95 ℃ of reactions 2 hours, aldehyde group content is surveyed in sampling, when aldehyde group content by mass ratio less than 2% the time, stopped reaction filters discharging.
3, the synthetic method of new type radiation solidified water-base resin according to claim 2 is characterized in that used alkaline reagents is sodium hydroxide or ammonium hydroxide or trolamine or triethylamine.
4, the synthetic method of new type radiation solidified water-base resin according to claim 2 is characterized in that used stopper is MEHQ or 2,6 ditertiary butyl p cresol or triphenylphosphine or Resorcinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100314207A CN1307266C (en) | 2005-04-05 | 2005-04-05 | New type radiation solidified aqueous resin and synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100314207A CN1307266C (en) | 2005-04-05 | 2005-04-05 | New type radiation solidified aqueous resin and synthetic method |
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| Publication Number | Publication Date |
|---|---|
| CN1687255A CN1687255A (en) | 2005-10-26 |
| CN1307266C true CN1307266C (en) | 2007-03-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100314207A Expired - Fee Related CN1307266C (en) | 2005-04-05 | 2005-04-05 | New type radiation solidified aqueous resin and synthetic method |
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| Country | Link |
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| CN (1) | CN1307266C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868580A (en) * | 2017-11-15 | 2018-04-03 | 惠州市凯辉化工有限公司 | A kind of water-based plastic cement ultraviolet-curing paint and its preparation and construction method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216094A (en) * | 1988-07-04 | 1990-01-19 | Sumitomo Chem Co Ltd | Heat-sensitive recording medium |
| JP2000001043A (en) * | 1998-06-12 | 2000-01-07 | Sekisui Chem Co Ltd | Recording material for water-base ink |
| CN1472198A (en) * | 2002-07-06 | 2004-02-04 | Continuous preparation of acetylene diureine |
-
2005
- 2005-04-05 CN CNB2005100314207A patent/CN1307266C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0216094A (en) * | 1988-07-04 | 1990-01-19 | Sumitomo Chem Co Ltd | Heat-sensitive recording medium |
| JP2000001043A (en) * | 1998-06-12 | 2000-01-07 | Sekisui Chem Co Ltd | Recording material for water-base ink |
| CN1472198A (en) * | 2002-07-06 | 2004-02-04 | Continuous preparation of acetylene diureine |
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| Publication number | Publication date |
|---|---|
| CN1687255A (en) | 2005-10-26 |
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