CN106589274B - A kind of high rate of closed hole melamine foams prepolymer and preparation method thereof - Google Patents
A kind of high rate of closed hole melamine foams prepolymer and preparation method thereof Download PDFInfo
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- CN106589274B CN106589274B CN201611192104.2A CN201611192104A CN106589274B CN 106589274 B CN106589274 B CN 106589274B CN 201611192104 A CN201611192104 A CN 201611192104A CN 106589274 B CN106589274 B CN 106589274B
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- prepolymer
- closed hole
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a kind of high rate of closed hole melamine foams prepolymers and preparation method thereof, belong to technical field of polymer materials, boron class modifying agent is added in the preparation process of melamine foams prepolymer, the methylol degree of functionality of melamine foams prepolymer after boron class modifier modification increases, and the electron deficient of boron atom increases the dehydrating condensation activity of methylol functional groups.In the foaming process of melamine resin, boron-modified melamine prepolymer energy fast reaction quickly forms the high polymer of crosslink density in the abscess surrounding that foaming agent is formed, stablizes and keep foam bubble, to prepare the melamine foams of high rate of closed hole, rate of closed hole reaches 95% or more.
Description
Technical field
The present invention relates to a kind of high rate of closed hole melamine foams prepolymers and preparation method thereof, belong to high polymer material technology neck
Domain.
Background technology
Melamino-formaldehyde foam also known as melamine foams plastics are the three dimensions nets that a kind of percent opening is up to 99% or more
The thermosets of shape structure.By steeping rib connection between its inner cell of the melamine foams of high opening rate, it is mutually communicated, therefore
The liquid such as water are easily accessible foam inside, and water absorption rate is higher, are unfavorable for the long-time service of foam, and reduce foam uses the longevity
Life；And a large amount of open-celled structures of foam inside so that cross-ventilation is serious, thermal coefficient is larger, it is made to be difficult to be used as a kind of guarantor
Adiabator.
To prepare the insulating foam of low water absorption, then solidification rate must be made preferably to be matched with expansion rate, from
And improve foam rate of closed hole.When non-modified melamine prepolymer is as thermosetting resin, solidification rate is too slow, is used to prepare
It is difficult to match with expansion rate when foamed material, therefore prepared melamine foams percent opening is high.In the type and use of foaming agent
Measure it is constant in the case of, solidification rate can be changed by the type and dosage that change curing agent, but pass through and change curing agent
Change being limited in scope for solidification rate, for specific system changes curing agent again after the dosage of curing agent reaches certain value
Dosage, solidification rate no longer varies widely, and both is difficult to make height changing the type and dosage of foaming agent again
Matching is not easy that the foamed material of high rate of closed hole is made.Dosage by changing boron modification agent can sensitive effectively broadening solidification speed
The adjustable range of rate enables solidification rate preferably to be matched with expansion rate when preparing foam, to obtain high rate of closed hole
Foamed material is used to have many advantages, such as low water absorption, low heat conductivity when fire-retardant heat insulation plate, is effectively improved the heat preservation of foam
Performance and service life.
Invention content
In view of the above existing problems in the prior art, the present invention provides a kind of high rate of closed hole melamine foams prepolymer and its systems
Preparation Method, prepolymer obtained can effectively prepare the melamine foams of high rate of closed hole, and rate of closed hole reaches 95% or more.
To achieve the goals above, a kind of high rate of closed hole melamine foams prepolymer that the present invention uses, the melamine foams are pre-
Boron class modifying agent is added in the preparation process of polymers, the melamine foams prepolymer viscosity after boron class modifier modification is in 5-
20Pas, solid content is in 50-65%, by the high rate of closed hole melamine foams prepolymer and emulsifier, foam stabilizer, foaming agent, solidification
Progress microwave foaming in mold is poured into agent after being mixed with certain proportion, obtained melamine foams rate of closed hole is 95% or more.
The present invention also provides a kind of preparation methods of above-mentioned high rate of closed hole melamine foams prepolymer, include the following steps：
1）The water of 100 parts by weight is weighed, the substance containing formaldehyde of 30-250 parts by weight, the pH value tune of 0.5-1 parts by weight is added
Agent is saved, stirring obtains formaldehyde substance aqueous solution in 75 DEG C of -90 DEG C of dissolving 10-30min；
2）Weigh 100 parts by weight steps 1）The pH value adjustment of 0.3-1 parts by weight is added in formaldehyde substance aqueous solution obtained
Agent, 25-100 parts by weight melamines, stirring, 40 DEG C of -60 DEG C of reaction 1-2h；The boron class modifying agent of 3-50 parts by weight is added,
In 40 DEG C of -60 DEG C of reaction 0.5-1h；The pH value adjustment agent of 0.5-3 parts by weight is added, is stirred, 65 DEG C of -85 DEG C of reaction 30-
50min；After reaction, the retarder of 0.3-1.5 parts by weight is added, is cooled to room temperature to get high rate of closed hole melamine foams
Prepolymer.
As an improvement, the step 1）In substance containing formaldehyde, using the formalin of 35-40%, metaformaldehyde, poly first
The mixing of one or more of aldehyde.
As an improvement, the step 1）Middle pH value adjustment agent is using the mixed of one or more of hydrochloric acid, formic acid, glacial acetic acid
It closes；
The step 2）The middle pH value adjustment agent being first added is using the mixed of one or more of sodium hydroxide, potassium hydroxide
It closes, the pH value adjustment agent being added afterwards uses the mixing of one or more of hexamethylenetetramine, ammonium hydroxide.
As an improvement, the step 2）In boron class modifying agent be boric acid, phenyl boric acid, one or more of borate
Mixing.
As an improvement, the step 2）In retarder be sodium tetraborate.
Compared with prior art, boron class modifying agent is added in the preparation process of melamine foams prepolymer of the invention, through boron
The methylol degree of functionality of melamine foams prepolymer after class modifier modification increases, and the electron deficient of boron atom increases hydroxyl first
The dehydrating condensation activity of base functional group.In the foaming process of melamine resin, boron-modified melamine prepolymer energy fast reaction,
The high polymer of crosslink density is quickly formed in the abscess surrounding that foaming agent is formed, stablizes and keeps foam bubble, to prepare
The melamine foams of high rate of closed hole.
The prepolymer clear of the high rate of closed hole melamine foams prepared, viscosity is in 5-20Pas, and solid content is in 50-
65%, the prepolymer Storage period of preparation is longer, after it is mixed with emulsifier, foam stabilizer, foaming agent, curing agent with certain proportion
Progress microwave foaming in mold is poured into, obtained melamine foams rate of closed hole is 95% or more.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, below by embodiment, to the present invention into
Row is further described.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
In limiting the scope of the invention.
Unless otherwise defined, all technical terms and scientific terms used herein are led with the technology for belonging to the present invention
The normally understood meaning of technical staff in domain is identical, and used term is intended merely to retouch in the description of the invention herein
State the purpose of specific embodiment, it is not intended that in the limitation present invention.
Embodiment one
A kind of preparation method of high rate of closed hole melamine foams prepolymer, includes the following steps：
1）100g water, the formalin of 135g 37%, 50g paraformaldehydes and 0.6g salt are added in 250ml three-necked flasks
Acid, stirring obtain formaldehyde substance aqueous solution after dissolving 20min at 80 DEG C；
2）100g steps 1 are added in 500ml three-necked flasks）Formaldehyde substance aqueous solution obtained, 0.3g sodium hydroxides,
Under stirring condition, 50g melamines are added at one time, are stirred, 50 DEG C of 1.5 h of reaction；6.5g boric acid, 1g phenyl boric acids and 1g is added
Borate reacts 0.5 h in 60 DEG C；0.8g hexamethylenetetramines, stirring, 65 DEG C of reactions 30min, 80 DEG C of reaction 5min are added；
After reaction, 0.8g sodium tetraborates are added, is cooled to room temperature, obtains the prepolymer of high rate of closed hole melamine foams.
The viscosity of the prepolymer of prepared high rate of closed hole melamine foams is in 15 Pas or so, clear, solid content
55% or so, the prepolymer Storage period of preparation is longer, by it with emulsifier, foam stabilizer, foaming agent, curing agent with certain proportion
Progress microwave foaming in mold is poured into after mixing, the rate of closed hole of obtained melamine foams is 98%.
Embodiment two
A kind of preparation method of high rate of closed hole melamine foams prepolymer, includes the following steps：
1）100g water, 50g metaformaldehydes, 50g paraformaldehydes and 0.8g formic acid are added in 250ml three-necked flasks, stirs,
After dissolving 30min at 90 DEG C, formaldehyde substance aqueous solution is obtained；
2）100g steps 1 are added in 500ml three-necked flasks）Formaldehyde substance aqueous solution obtained, 0.3g potassium hydroxide,
Under stirring condition, 40g melamines are added at one time, are stirred, 55 DEG C of 1.5 h of reaction；Be added 13.8g boric acid, 1g phenyl boric acids and
0.5g borates react 1 h in 40 DEG C；0.8g ammonium hydroxide, stirring, 70 DEG C of reactions 30min, 85 DEG C of reaction 5min are added；Reaction knot
Shu Hou is added 1.2 g sodium tetraborates, is cooled to room temperature, obtains the prepolymer of high rate of closed hole melamine foams.
The viscosity of the prepolymer of prepared high rate of closed hole melamine foams is in 20 Pas or so, clear, solid content
65% or so, the prepolymer Storage period of preparation is longer, by it with emulsifier, foam stabilizer, foaming agent, curing agent with certain proportion
Progress microwave foaming in mold is poured into after mixing, the rate of closed hole of obtained melamine foams is 95%.
Embodiment three
A kind of preparation method of high rate of closed hole melamine foams prepolymer, includes the following steps：
1）100g water, the formalin of 125g 40%, 50g paraformaldehydes and 0.6g salt are added in 250ml three-necked flasks
Acid, stirring obtain formaldehyde substance aqueous solution after dissolving 15min at 85 DEG C；
2）100g steps 1 are added in 500ml three-necked flasks）Formaldehyde substance aqueous solution obtained, 0.3g sodium hydroxides,
Under stirring condition, 40g melamines are added at one time, are stirred, 45 DEG C of reaction 1h；2.25g boric acid, 0.5g phenyl boric acids and 1g is added
Borate reacts 0.5 h in 50 DEG C；0.8g hexamethylenetetramines, stirring, 65 DEG C of reactions 25min, 80 DEG C of reaction 10min are added；
After reaction, 0.3g sodium tetraborates are added, is cooled to room temperature, obtains the prepolymer of high rate of closed hole melamine foams.
In 5 Pas or so, clear, solid content exists the viscosity of the prepolymer of prepared high rate of closed hole melamine foams
50% or so, the prepolymer Storage period of preparation is longer, itself and emulsifier, foam stabilizer, foaming agent, curing agent are mixed with certain proportion
Progress microwave foaming in mold is poured into after conjunction, the rate of closed hole of obtained melamine foams is 96%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (5)
1. a kind of preparation method of high rate of closed hole melamine foams prepolymer, which is characterized in that include the following steps：
1）The water of 100 parts by weight is weighed, the pH values of substance containing formaldehyde, 0.5-1 parts by weight that 30-250 parts by weight are added are adjusted
Agent, stirring obtain formaldehyde substance aqueous solution in 75 DEG C of -90 DEG C of dissolving 10-30min；
2）Weigh 100 parts by weight steps 1）Formaldehyde substance aqueous solution obtained, the pH values conditioning agent of addition 0.3-1 parts by weight,
25-100 parts by weight melamines, stirring, 40 DEG C of -60 DEG C of reaction 1-2h；The boron class modifying agent for adding 3-50 parts by weight, in 40
DEG C of -60 DEG C reaction 0.5-1h；The pH value adjustment agent of 0.5-3 parts by weight is added, is stirred, 65 DEG C of -85 DEG C of reaction 30-50min；Instead
After answering, the retarder of 0.3-1.5 parts by weight is added, is cooled to room temperature to get the prepolymer of high rate of closed hole melamine foams.
2. a kind of preparation method of high rate of closed hole melamine foams prepolymer as described in claim 1, which is characterized in that the step
Rapid 1）In substance containing formaldehyde, using the mixing of one or more of the formalin of 35-40%, metaformaldehyde, paraformaldehyde.
3. a kind of preparation method of high rate of closed hole melamine foams prepolymer as described in claim 1, which is characterized in that the step
Rapid 1）Middle pH values conditioning agent uses the mixing of one or more of hydrochloric acid, formic acid, glacial acetic acid；
The step 2）The middle pH value adjustment agent being first added uses the mixing of one or more of sodium hydroxide, potassium hydroxide,
The pH value conditioning agents being added afterwards use the mixing of one or more of hexamethylenetetramine, ammonium hydroxide.
4. a kind of preparation method of high rate of closed hole melamine foams prepolymer as described in claim 1, which is characterized in that the step
Rapid 2）In boron class modifying agent be boric acid, phenyl boric acid, one or more of borate mixing.
5. a kind of preparation method of high rate of closed hole melamine foams prepolymer as described in claim 1, which is characterized in that the step
Rapid 2）In retarder be sodium tetraborate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611192104.2A CN106589274B (en) | 2016-12-21 | 2016-12-21 | A kind of high rate of closed hole melamine foams prepolymer and preparation method thereof |
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| CN201611192104.2A CN106589274B (en) | 2016-12-21 | 2016-12-21 | A kind of high rate of closed hole melamine foams prepolymer and preparation method thereof |
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| CN107474207B (en) * | 2017-08-31 | 2019-06-11 | 浙江亚迪纳新材料科技股份有限公司 | The preparation process of low-methoxyl aldehyde melamine foam |
| CN108047645B (en) * | 2017-12-22 | 2020-02-07 | 合肥工业大学 | Melamine foam prepared by using blocked isophorone diisocyanate as curing agent |
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| CN101671472A (en) * | 2008-09-09 | 2010-03-17 | 上海昊海化工有限公司 | Resin solution for preparing melamine formaldehyde resin foam plastics and preparation method thereof |
| CN104277416B (en) * | 2013-07-03 | 2017-11-03 | 合肥杰事杰新材料股份有限公司 | A kind of modified cyanurotriamide foamed plastics and preparation method thereof |
| CN104530340B (en) * | 2014-12-22 | 2016-06-29 | 沙县宏盛塑料有限公司 | A kind of preparation method of boron modification melamine resin |
| CN104774427B (en) * | 2015-05-07 | 2016-03-02 | 成都玉龙化工有限公司 | A kind of soft melamine foamed plastic of high-density and preparation method |
| CN105693965B (en) * | 2016-03-18 | 2018-06-19 | 江南大学 | A kind of rigid closed cell melamine foam and preparation method thereof |
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