CN106243335B - Inorganic hybridization polyester polyol etherified melamine polyimide resin and preparation method thereof - Google Patents

Inorganic hybridization polyester polyol etherified melamine polyimide resin and preparation method thereof Download PDF

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CN106243335B
CN106243335B CN201610618837.1A CN201610618837A CN106243335B CN 106243335 B CN106243335 B CN 106243335B CN 201610618837 A CN201610618837 A CN 201610618837A CN 106243335 B CN106243335 B CN 106243335B
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polyester polyol
inorganic hybridization
polyimide resin
etherified melamine
melamine polyimide
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CN106243335A (en
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王洪波
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Changzhou Poly Energy Saving Technology Co Ltd
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Changzhou Poly Energy Saving Technology Co Ltd
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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Abstract

The invention belongs to inorganic hybridization technical field of polymer materials, more particularly to a kind of inorganic hybridization polyester polyol etherified melamine polyimide resin and preparation method thereof.It mainly includes the following steps that：(1) etherification reaction, hexamethylolmelamine is added into reaction kettle and polyester polyol carries out insulation reaction, obtains four etherificates or five etherificate melmacs；(2) alkali neutralization；(3) hydridization is reacted；(4) cold filtration obtains finished product.Inorganic hybridization polyester polyol etherified melamine polyimide resin made from the method through the invention, by being reacted with the hybrid cross-linked of inorganic hybridization compound, so that the amino resins polyalcohol ultimately generated introduces the heat-resistant fireproofs element such as boron, molybdenum, antimony, to improve the high temperature resistance and flame retardant property of amino resins polyalcohol, it is mainly used in and prepares combined polyether and paint.

Description

Inorganic hybridization polyester polyol etherified melamine polyimide resin and preparation method thereof
Technical field
The invention belongs to inorganic hybridization technical field of polymer materials, more particularly to a kind of inorganic hybridization polyester polyols alcohol ether Change melmac with and preparation method thereof.
Background technology
Since amino resins has certain heat resistance, so in many fields, including coating industry, furniture industry, Polyurethane industries among others etc. have application.But applied on the polyurethane material of high fire-retardance, high temperature resistance still has certain Gap.
Due to the special construction of polyurethane foam plastics molecule, determine its be easy burning, non-refractory characteristic.With The continuous popularization and application of polyurethane energy-saving heat preserving hard bubble application technology, the requirement to its flame retardant property is also higher and higher, especially GB8624-2012《Classification on burning behaviour for building materials》And GB50016-2014《Code for fire protection design of buildings》Promulgation it is real Shi Hou, polyurethane foam are conveniently faced with acid test in fire retardant performance.Therefore, the resistance to height of amino resins how is improved Mild flame retardant property is at urgent technical problem to be solved in the field.
Invention content
In order to solve the above problem of the existing technology, the present invention provides a kind of inorganic hybridization polyester polyols are etherified Melmac and preparation method thereof, using hexamethylolmelamine as raw material, under the conditions of acid medium, with polyester polyols Alcohol reaction generates tetramethyl etherified melamine polyimide resin or five methyl-etherified melmacs, then is carried out instead with inorganic hybridization compound It answers, generates inorganic hybridization polyester polyol etherified melamine polyimide resin, there is higher flame retardant property and high temperature resistance.
The technical solution adopted in the present invention is as follows：
Inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, one kind in B or Sb；
R in the molecular structure is
Wherein 1≤n≤32.
The preparation method of the inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：Main packet Include following steps：
Under the conditions of acid medium, by hexamethylolmelamine and claim 1 R represent polyester polyol into Row etherification reaction obtains polyester polyol etherified melamine polyimide resin, and under agitation plus alkali carries out alkali neutralization reaction；
It is small that the melmac of etherificate with inorganic hybridization compound under conditions of 100~110 DEG C is reacted 0.5~2 When, hydridization reaction is completed, and is cooled to 60~80 DEG C, salt is filtered out with filter, obtain inorganic hybridization polyester polyols etherified three Cymel.
The preparation method of the inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：Including with Lower specific steps：
(1) etherification reaction
The polyester polyol that the R being added into reaction kettle in hexamethylolmelamine and claim 1 is represented, acid adding tune It is 2.5~5.5 to save pH, and under conditions of 35~65 DEG C, 30~120min of heat preservation carries out etherification reaction, obtains polyester polyols alcohol ether Change melmac；
(2) alkali neutralization
It is stirred under the conditions of 40~80 revs/min of rotating speed, it is 8.0~9.0 to add alkali to adjust pH, which protects It holds temperature and is less than 50 DEG C；
(3) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, is warming up to 100~110 DEG C and reacts 1~2 hour, hydridization is anti- It should complete；
(4) cold filtration
60~80 DEG C are cooled to, 2%~2.5% super-cell is added, filters out salt with filter, obtains inorganic miscellaneous Change polyester polyol etherified melamine polyimide resin.
The preparation method of the inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：The step Suddenly the inorganic hybridization compound in (3) is：Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water, eight Boratex, three oxygen Change one kind in two antimony, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate.
The preparation method of the inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：The step Suddenly (1) or middle adjust sour used in pH of step (2) are hydrochloric acid or nitric acid, and mass concentration is 31~36%, and alkali used is hydroxide Sodium, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, mass concentration are 25~35%.
The preparation method of the inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：The step Suddenly the polyester polyol in (1) is phthalic anhydride diethylene glycol copolymer, phthalic anhydride glycerine copolymer or phthalic anhydride pentaerythrite copolymer In one kind.
The application of the inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：It is described inorganic miscellaneous Change polyester polyol etherified melamine polyimide resin and be used to prepare combined polyether, the combined polyether includes use for hard bubble of polyurethane combination Polyethers, polyurethane semihard foam combined polyether, soft polyurethane foam combined polyether.
The application of the inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：It is described inorganic miscellaneous Change polyester polyol etherified melamine polyimide resin and be used to prepare paint, the paint includes alkyd paint coating, gathers Urethane paint, epoxy resin paint coating, acrylic paint coating, amino paint.
The inorganic hybridization reaction principle of patent of the present invention：
The principle reacted can be crosslinked with boron, molybdenum, antimony element using the methylol contained in compound, realize this hair The hydridization reaction process of bright patent eliminates reactive group because enclosing methylol, and the temperature in reaction process can be substantially Degree improves and introduces boron, molybdenum, antimony ignition-proof element to 110 DEG C, and on molecular structure so that stability, the flame retardant property of product It is substantially improved with high temperature resistance.
The above-mentioned technical proposal of the present invention compared with prior art, has the following advantages：
1, it is reacted with the hybrid cross-linked of inorganic hybridization compound by the melmac of etherificate so that ultimately generate Melmac polyester polyol introduces the heat-resistant fireproofs element such as boron, antimony, molybdenum, more to improve amino resins polyester The high temperature resistance and flame retardant property of first alcohol, compared with the resin before non-hydridization, 50 DEG C of high temperature resistance raising or more is fire-retardant Performance improves at least 20%.
2, the preparation of the inorganic hybridization polyester polyol etherified melamine polyimide resin overcomes the etherified trimerization of polyester polyols Melamine resin molecular structure introduces the technical barrier of ignition-proof element, solves outer addition fire retardant to product physical mechanical property The technical problems such as influence and flame retardant effect are undesirable.
3, it is prepared into heat-resistant fireproof melmac polyester polyol with this heat-resistant fireproof melmac, with Isocyanates MDI reactions, the inorganic hybridization polyurethane with melamine foamed material excellent physical properties of formation, intensity is high, does not send out Powder, not modification are fully achieved that GB50404-2007 standards are waterproof thermal-insulated and the B1 grades of fire-retardant requirements of GB8624-2012 standards. While ensureing physical property, excellent fireproof performance, oxygen index (OI) is more than 30%.
4, since prepared melmac polyester polyol has high flame resistance and high temperature resistance, so When producing polyurethane foam with it, expensive high fire-retardance phosphate flame retardant need not be used, makes foam cost greatly It reduces, reduces 30% or more, economy is more reasonable.
Specific implementation mode
With reference to specific embodiment, the present invention will be described in detail, but the invention is not limited in specific embodiments.
Embodiment 1
Boron hydridization phthalic anhydride diethylene glycol is etherified the preparation of melmac
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and phthalic anhydride diethylene glycol are added in reaction kettle, it is 2.5 to add acid for adjusting pH, at 35 DEG C Under the conditions of, mixing speed is that 60 revs/min of heat preservation 120min carry out etherification reaction, obtains phthalic anhydride diethylene glycol etherificate melamine Resin；
(2) alkali neutralization
It is stirred under the conditions of 40 revs/min of rotating speed, it is 8.0 to add alkali to adjust pH, which keeps temperature low In 50 DEG C；
(3) hydridization is reacted
Four water, eight Boratex and water are added into reaction kettle, is warming up to 100 DEG C and reacts 2 hours, hydridization reaction is completed；
(4) cold filtration
60 DEG C are cooled to, 2% super-cell is added, filters out salt with filter, obtains boron hydridization phthalic anhydride diethyl two Etherified melmac.
Embodiment 2
The preparation of stilba phthalic anhydride glycerine etherified melamine polyimide resin
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and phthalic anhydride glycerine are added in reaction kettle, it is 5.5 to add acid for adjusting pH, in 65 DEG C of item Under part, mixing speed is 80 revs/min, and heat preservation 30min carries out etherification reaction, obtains phthalic anhydride glycerine etherified melamine amine tree Fat；
(2) alkali neutralization
It is stirred under the conditions of 80 revs/min of rotating speed, it is 9.0 to add alkali to adjust pH, which keeps temperature low In 50 DEG C；
(3) hydridization is reacted
Antimony oxide and water are added into reaction kettle, is warming up to 110 DEG C and reacts 0.5 hour, hydridization reaction is completed；
(4) cold filtration
It is cooled to 80 DEG C, 2.5% super-cell is added, salt is filtered out with filter, obtain stilba phthalic anhydride the third three Etherified melmac.
Embodiment 3
Boron hydridization phthalic anhydride diethylene glycol is etherified the preparation of melmac
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and phthalic anhydride diethylene glycol are added in reaction kettle according to the above ratio, add the acid for adjusting pH to be 3.0, under conditions of 45 DEG C, mixing speed is 650 revs/min, and heat preservation 70min carries out etherification reaction, obtains phthalic anhydride diethyl two Etherified melmac；
(2) alkali neutralization
It is stirred under the conditions of 50 revs/min of rotating speed, it is 8.5 to add alkali to adjust pH, which keeps temperature low In 50 DEG C；
(3) hydridization is reacted
Four water, eight Boratex and water are added into reaction kettle, is warming up to 100 DEG C and reacts 1 hour, hydridization reaction is completed；
(4) cold filtration
70 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtains boron hydridization phthalic anhydride diethyl Glycol is etherified melmac.
Embodiment 4
The preparation of molybdenum hydridization phthalic anhydride pentaerythrite etherified melamine polyimide resin
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and phthalic anhydride pentaerythrite are added in reaction kettle, it is 4.0 to add acid for adjusting pH, at 40 DEG C Under the conditions of, mixing speed is 70 revs/min, and heat preservation 90min carries out etherification reaction, obtains phthalic anhydride pentaerythrite etherified melamine amine Resin；
(2) alkali neutralization
It is stirred under the conditions of 60 revs/min of rotating speed, it is 8.5 to add alkali to adjust pH, which keeps temperature low In 50 DEG C；
(3) hydridization is reacted
Sodium molybdate and water are added into reaction kettle, is warming up to 105 DEG C and reacts 1 hour, hydridization reaction is completed；
(4) cold filtration
70 DEG C are cooled to, 2.5% super-cell is added, filters out salt with filter, obtains molybdenum hydridization phthalic anhydride season penta Tetrol etherified melamine polyimide resin.
Embodiment 5
The preparation of molybdenum hydridization phthalic anhydride glycerine etherified melamine polyimide resin
Molecular structural formula：
(1) etherification reaction
Hexamethylolmelamine and phthalic anhydride glycerine are added in reaction kettle, it is 4.0 to add acid for adjusting pH, in 60 DEG C of item Under part, mixing speed is 70 revs/min, and heat preservation 110min carries out etherification reaction, obtains phthalic anhydride glycerine etherified melamine amine tree Fat；
(2) alkali neutralization
It is stirred under the conditions of 50 revs/min of rotating speed, it is 8.5 to add alkali to adjust pH, which keeps temperature low In 50 DEG C；
(3) hydridization is reacted
Boratex and water are added into reaction kettle, is warming up to 105 DEG C and reacts 1.5 hours, hydridization reaction is completed；
(4) cold filtration
It is cooled to 60 DEG C, 2.5% super-cell is added, salt is filtered out with filter, obtain molybdenum hydridization phthalic anhydride the third three Etherified melmac.

Claims (8)

1. inorganic hybridization polyester polyol etherified melamine polyimide resin, it is characterised in that：Molecular structure is as follows：
X in the molecular structure is inorganic hybridization element, one kind in B or Sb；
R in the molecular structure is
Wherein 1≤n≤32.
2. the preparation method of inorganic hybridization polyester polyol etherified melamine polyimide resin as described in claim 1, feature exist In：It mainly includes the following steps that：
Under the conditions of acid medium, the polyester polyol that the R in hexamethylolmelamine and claim 1 is represented carries out ether Polyester polyol etherified melamine polyimide resin is obtained by the reaction in change, and under agitation plus alkali carries out alkali neutralization reaction；
The melmac of etherificate is reacted 0.5~2 hour with inorganic hybridization compound under conditions of 100~110 DEG C, it is miscellaneous Change reaction to complete, is cooled to 60~80 DEG C, salt is filtered out with filter, obtain inorganic hybridization polyester polyol etherified melamine amine Resin.
3. the preparation method of inorganic hybridization polyester polyol etherified melamine polyimide resin as claimed in claim 2, feature exist In：Including step in detail below：
(1) etherification reaction
The polyester polyol that the R being added into reaction kettle in hexamethylolmelamine and claim 1 is represented, adds acid for adjusting pH It is 2.5~5.5, under conditions of 35~65 DEG C, 30~120min of heat preservation carries out etherification reaction, obtains polyester polyols etherified three Cymel；
(2) alkali neutralization
It is stirred under the conditions of 40~80 revs/min of rotating speed, it is 8.0~9.0 to add alkali to adjust pH, which keeps temperature Degree is less than 50 DEG C；
(3) hydridization is reacted
Inorganic hybridization compound and water are added into reaction kettle, is warming up to 100~110 DEG C and reacts 1~2 hour, hydridization has been reacted At；
(4) cold filtration
60~80 DEG C are cooled to, 2%~2.5% super-cell is added, salt is filtered out with filter, it is poly- to obtain inorganic hybridization Ester polyol etherified melamine polyimide resin.
4. the preparation method of inorganic hybridization polyester polyol etherified melamine polyimide resin according to claim 3, feature It is：Inorganic hybridization compound in the step (3) is：Boratex, potassium borate, boric acid, zinc borate, boron phosphate, four water eight In Boratex, antimony oxide, antimony pentoxide, sodium molybdate, potassium molybdate, zinc molybdate, ammonium molybdate, ammonium tetramolybdate or ammonium heptamolybdate One kind.
5. the preparation method of inorganic hybridization polyester polyol etherified melamine polyimide resin according to claim 3, feature It is：It is hydrochloric acid or nitric acid that acid used in pH is adjusted in the step (1) or step (2), and mass concentration is 31~36%, used Alkali is sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide or potassium carbonate, and mass concentration is 25~35%.
6. the preparation method of inorganic hybridization polyester polyol etherified melamine polyimide resin according to claim 3, feature It is：Polyester polyol in the step (1) is phthalic anhydride diethylene glycol copolymer, phthalic anhydride glycerine copolymer or phthalic anhydride season penta One kind in four alcohol copolymers.
7. the application of inorganic hybridization polyester polyol etherified melamine polyimide resin according to claim 1, it is characterised in that： The inorganic hybridization polyester polyol etherified melamine polyimide resin is used to prepare combined polyether, and the combined polyether includes polyurethane Hard bubble combined polyether, polyurethane semihard foam combined polyether, soft polyurethane foam combined polyether.
8. the application of inorganic hybridization polyester polyol etherified melamine polyimide resin according to claim 1, it is characterised in that： The inorganic hybridization polyester polyol etherified melamine polyimide resin is used to prepare paint, and the paint includes alkyd oil Paint coating, high concentrations of toluene diisocyanate coating, epoxy resin paint coating, acrylic paint coating, amino paint.
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CN101712749A (en) * 2009-11-19 2010-05-26 中国科学院广州化学研究所 Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof
CN102690661A (en) * 2012-06-07 2012-09-26 常州大学 Hybrid fire retardant and preparing method thereof
CN104987484A (en) * 2015-05-29 2015-10-21 张家港迪蒙德节能科技有限公司 Inorganic material hybrid hard melamine polyurethane foam heat insulation material, preparation method thereof and combined polyether used therein

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CN101712749A (en) * 2009-11-19 2010-05-26 中国科学院广州化学研究所 Silicon nitride hybridization type epoxy resin curing agent and preparation method and application thereof
CN102690661A (en) * 2012-06-07 2012-09-26 常州大学 Hybrid fire retardant and preparing method thereof
CN104987484A (en) * 2015-05-29 2015-10-21 张家港迪蒙德节能科技有限公司 Inorganic material hybrid hard melamine polyurethane foam heat insulation material, preparation method thereof and combined polyether used therein

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