CN108440764A - A kind of preparation method of hyperbranched type melamine cyanurate flame retardant and its application in PA6 materials - Google Patents
A kind of preparation method of hyperbranched type melamine cyanurate flame retardant and its application in PA6 materials Download PDFInfo
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- CN108440764A CN108440764A CN201810222755.4A CN201810222755A CN108440764A CN 108440764 A CN108440764 A CN 108440764A CN 201810222755 A CN201810222755 A CN 201810222755A CN 108440764 A CN108440764 A CN 108440764A
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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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The present invention relates to technical field of flame retardant, more particularly to a kind of hyperbranched type MCA fire retardants, the hydroxyl in Hyperbranched Polymer with Terminal Hydroxyl and TDI polymerizations, then prepares with tradition the raw material melamine of MCA and react, obtain hyperbranched type melamine.Hyperbranched type MCA fire retardants are obtained by the reaction in obtained hyperbranched type melamine and cyanuric acid under certain condition.AB is prepared by selection2The raw material of monomer and selection introduce isocyanate group, charring rate of fire retardant during fire-retardant is promoted, and the compatibility of relatively large molecular weight and high molecular material can improve, can be good at the flame retarding efficiency for promoting fire retardant, increase flame retardant effect, and reduces additive amount.
Description
Technical field
The present invention relates to technical field of flame retardant, more particularly to a kind of hyperbranched type melamine cyanurate flame retardant,
Further relate to preparation method and its application in PA6 materials.
Background technology
With the development of society, high molecular material gradually replaces traditional material, it is widely used in chemical industry, electronics is mechanical,
The multiple fields such as aviation, still, high molecular material are typically all inflammable or flammable, are easy to cause fire incident.In order to solve
The resistance to combustion of synthetic material presses down the problems such as cigarette, it is ensured that the safety that synthetic material uses, most efficient method are to add people's fire retardant.
Recently as people's environmental consciousness enhancing and a series of environmental regulations formulation, such as European Union publication《About in electronics
The instruction of certain harmful substances is forbidden to use in electrical equipment》, it is specified that the fire retardant of the halogen class in part cannot be used in engineering plastic
On the product of material, European market is especially fierce to this reflection, and phase is made to the use of halogen material one after another by many transnational major companies
The limitation answered, this largely promotes the non-halogen fire-retardant process of material.Thus halogen-free flame retardants due to it is nontoxic, without dirt
The characteristics such as dye, increasingly have been favored by people in recent years.In order to meet the needs in market and comply with the demand for development in epoch,
Adhere to developing and oneself becomes inexorable trend using halogen-free smoke resistance flame resistance agent.
According to statistics, in non-reinforced PA6, nearly 50% is MCA（Melamine cyanurate）Flame retardant products.Nitrogen system hinders
Combustion agent has many good qualities:Highly effective flame-retardant, be halogen-free, non-corrosive effect, thermal stability height etc..MCA changes 6 hot oxygen of nylon
The course of degradation, i.e. the two interaction make surface form carbonization expansion, thus propose the fire retardation of MCA fire-retardant Nylon 6s
It is that condensed phase catalysis carbonization expands the fire-retardant mechanism of action of gentle phase dilution.Nitrogen system has with other fire retardants cooperates with work well
With, therefore there are good market prospects.But a large amount of MCA is added applied to the fire-retardant needs of PA6 and can be only achieved preferably
Flame retardant effect can increase use cost, it is therefore desirable to which modified MC A makes its addition become smaller, and can preferably improve PA6's
Flame retardant property improves the limit oxygen index of PA6.
Highly branched dendritic macromole is one of the hot spot of recent decades research, the hyperbranched poly as its homologue
Close object because its own the advantages of such as：Active site is more, and viscosity is small, and three are netted, good with matrix amalgamation, photoelectric material,
The fields such as coating, adhesive, drug carrier have broad application prospects.
Invention content
In order to solve that the cost of production flame-proof PA 6 can be increased when MCA uses dosage big as PA6 fire retardants, improve PA6's
Flame retardant property, a kind of the present invention provides flame retardant properties more excellent, the lower hyperbranched type MCA of cost.
The present invention also provides the method for the dissaving polymer modified MC A and the applications in PA6.
The present invention is achieved by the following measures：
What a kind of hyperbranched MCA was obtained through the following steps：
（1）Hyperbranched Polymer with Terminal Hydroxyl progress is terminal-modified, introduces toluene di-isocyanate(TDI), it is isocyanates to obtain to end
Dissaving polymer and melamine polymerize to obtain hyperbranched type melamine；
（2）Hyperbranched type melamine and cyanuric acid is soluble in water that suspension is made is then small in 100 DEG C of -120 DEG C of stoichiometric numbers
When, after slurry become slit it is thick after the reaction was continued a period of time, using filter, drying, broken obtain the finished product of hyperbranched type MCA.
AB is obtained by the reaction with phthalic anhydride and two different hydramine in the hyperbranched type MCA fire retardants2Type monomer, with three hydroxyls
Methylpropane makees core molecule, AB2Type monomer is reacted with core molecule, then, is added what toluene di-isocyanate(TDI) (TDI) modification obtained
End group be isocyanates dissaving polymer, itself and melamine be obtained by the reaction to the melamine of hyperbranched type, then and
Raw material cyanuric acid is soluble in water to be made suspension, then 100 DEG C -120 DEG C reaction a few hours, after slurry become slit it is thick after continue
Reaction a period of time using filter, drying, broken obtains the finished product of hyperbranched type MCA.
The branch terminals of the hyperbranched type fire retardant, preferably hyperbranched polyamine -ester contain a large amount of melamine cyanogen
Lithate.
The hyperbranched type MCA fire retardants, the core molecule and AB of superbrnaching end-hydroxy polyamine -ester2Monomer is according to 1：9、
1：21 or 1：Second generation terminal hydroxy group polyamine -ester, third generation terminal hydroxy group polyamine -ester or the forth generation that 45 molar ratio reactions respectively obtain
Terminal hydroxy group polyamine -ester.
The hyperbranched type MCA fire retardants, superbrnaching end-hydroxy polyamine -ester and TDI are according to 1：12、1：24 or 1：48 rub
You are the super of isocyanates than to react the second generation end that respectively obtains be the dissaving polymer of isocyanates, third generation end
Branched polymer or forth generation end are the dissaving polymers of isocyanates.
The hyperbranched type MCA fire retardants, melamine and end are the dissaving polymer and trimerization of isocyanates
Cyanamide polymerize according to 1：12、1：24 or 1：The hyperbranched melamine of the second generation that 48 molar ratio reactions respectively obtain, the third generation are super
Branched melamine and the hyperbranched melamine of forth generation.
The hyperbranched type MCA fire retardants, hyperbranched type melamine and cyanuric acid are according to 1：12、1：24 or 1：48 rub
You overspend type MCA fire retardants more hyperbranched than the second generation that reaction respectively obtains, the hyperbranched type MCA fire retardants of the third generation and forth generation
Change type MCA fire retardants.
The AB2It according to molar ratio is 1 that monomer, which is by phthalic anhydride and two different hydramine,：1 synthesis.
The additive amount of the hyperbranched type MCA fire retardants, preferred hyperbranched type MCA fire retardants is that PA material feedstocks are total
The 6~12% of quality.
The specific synthetic method of hyperbranched type MCA fire retardants：
(1)AB2The synthesis of monomer
The phthalic anhydride of equimolar amounts and two different hydramine reactions：
(2) synthesis of Hyperbranched Polymer with Terminal Hydroxyl
Trimethylolpropane and AB2Monomer reaction：
。
(3) Hyperbranched Polymer with Terminal Hydroxyl reacts the dissaving polymer that synthesis end is isocyanates with TDI：
。
（4）End is the dissaving polymer of isocyanates and the melamine of hyperbranched type is obtained by the reaction in melamine：
。
（5）Hyperbranched type MCA fire retardants are obtained by the reaction in the melamine and cyanuric acid of hyperbranched type：
。
The hyperbranched type MCA fire retardants, core molecule is trimethylolpropane, at this point, core molecule and AB2Mole of monomer
Than being 1：3~45.
The hyperbranched type MCA fire retardants, the hyperbranched type fire retardant core molecule of the first generation, the second generation, the third generation, forth generation
With AB2The molar ratio of monomer is respectively 1：3、1：9、1：21、1：45.
The molar ratio of the hyperbranched type MCA fire retardants, core molecule and TDI are 1：6、1：12、1：24、1：48.
The present invention provides a kind of hyperbranched type fire retardant, carbon source in conventional flame retardant is changed in the form of hyperbranched is
The drawbacks of small molecule, and carbon source and air source are combined, it is blocked with acid source, makes carbon source, air source, the acid source Trinity, be made
A kind of hyperbranched type fire retardant haveing excellent performance.
Beneficial effects of the present invention：
1, the present invention is that AB is made with the reactions such as phthalic anhydride and two different hydramine2The presence of monomer, phenyl ring can promote resistance
Charring rate of agent during fire-retardant is fired, and the compatibility of relatively large molecular weight and high molecular material can improve, it can
The flame retarding efficiency of fire retardant is promoted well；
2, AB is prepared by selection2The raw material of monomer, synthesis of super branched type MCA fire retardants promote fire retardant during fire-retardant
Charring rate；And the compatibility of relatively large molecular weight and high molecular material can improve；
3, it is all by the object of polyalcohol and isocyanates base class that the end used in the present invention, which is the dissaving polymer of isocyanates,
Made from qualitative response and melamine reaction synthesizes a kind of hyperbranched type melamine, can preferably promote the resistance of fire retardant
Fuel efficiency rate increases flame retardant effect, and reduces additive amount.
Specific implementation mode
More to be stated in detail to specific implementation method of the present invention below, it is therefore intended that illustrate the present invention design and
Feature, it is not intended to limit the scope of the present invention.Any equivalent change or modification in accordance with the spirit of the invention,
It should be covered by the protection scope of the present invention.
Implementation one
(1) phthalic anhydride is accurately weighed with electronic balance, is dissolved in n,N-dimethylacetamide（DMAc）, it is placed in beaker
In, fully dissolve.Two different hydramine are added into three-necked flask, stir evenly.The phthalic anhydride fully dissolved is instilled three
In mouth flask, 3 h are reacted under room temperature, obtain AB2Monomer.
（2）Toluene is first added in above-mentioned system, weighs trimethylolpropane, so that it is fully dissolved with a small amount of DMAc, so
After be added in three-necked flask, add p-methyl benzenesulfonic acid, be heated to 130 DEG C of condensing refluxes, have in spherical condensation tube reflux produce
It is raw, insulation reaction 7-8h.
（3）TDI is added into dissaving polymer obtained above, and p-methyl benzenesulfonic acid is added and makees catalyst, stirs
Uniformly, constant temperature successive reaction 6 hours, vacuum distillation.It must be the dissaving polymer of isocyanates to end.
（4）Melamine, and addition pair are added in the dissaving polymer for end obtained above being isocyanates
Toluenesulfonic acid makees catalyst, stirs evenly, constant temperature successive reaction 4 hours, vacuum distillation.Obtain the melamine of hyperbranched type.
（5）Hyperbranched type melamine and cyanuric acid is soluble in water that suspension is made, then in 100 DEG C of -120 DEG C of reactions
A few hours, after slurry become slit it is thick after the reaction was continued a period of time, using filter, drying, it is broken obtain hyperbranched type MCA at
Product.
（6）It is added to the 6% of hyperbranched type MCA fire retardants PA6 material gross masses obtained above, synthesis has resistance
Fire the material of performance.Sample is prepared according to standard GB/T 2406.2-2009 and measures its flame retardant property limit oxygen index.
Implementation two
(1) phthalic anhydride is accurately weighed with electronic balance, is dissolved in n,N-dimethylacetamide（DMAc）, it is placed in beaker
In, fully dissolve.Two different hydramine are added into three-necked flask, stir evenly.The phthalic anhydride fully dissolved is instilled three
In mouth flask, 3 h are reacted under room temperature, obtain AB2Monomer.
（2）Toluene is first added in above-mentioned system, weighs trimethylolpropane, so that it is fully dissolved with a small amount of DMAc, so
After be added in three-necked flask, add p-methyl benzenesulfonic acid, be heated to 130 DEG C of condensing refluxes, have in spherical condensation tube reflux produce
It is raw, insulation reaction 7-8h.
（3）TDI is added into dissaving polymer obtained above, and p-methyl benzenesulfonic acid is added and makees catalyst, stirs
Uniformly, constant temperature successive reaction 6 hours, vacuum distillation.It must be the dissaving polymer of isocyanates to end.
（4）Melamine, and addition pair are added in the dissaving polymer for end obtained above being isocyanates
Toluenesulfonic acid makees catalyst, stirs evenly, constant temperature successive reaction 4 hours, vacuum distillation.Obtain the melamine of hyperbranched type.
（5）Hyperbranched type melamine and cyanuric acid is soluble in water that suspension is made, then in 100 DEG C of -120 DEG C of reactions
A few hours, after slurry become slit it is thick after the reaction was continued a period of time, using filter, drying, it is broken obtain hyperbranched type MCA at
Product.
（6）It is added to the 8% of hyperbranched type MCA fire retardants PA6 material gross masses obtained above, synthesis has resistance
Fire the material of performance.Sample is prepared according to standard GB/T 2406.2-2009 and measures its flame retardant property limit oxygen index.
Implementation three：
(1) phthalic anhydride is accurately weighed with electronic balance, is dissolved in n,N-dimethylacetamide（DMAc）, it is placed in beaker
In, fully dissolve.Two different hydramine are added into three-necked flask, stir evenly.The phthalic anhydride fully dissolved is instilled three
In mouth flask, 3 h are reacted under room temperature, obtain AB2Monomer.
（2）Toluene is first added in above-mentioned system, weighs trimethylolpropane, so that it is fully dissolved with a small amount of DMAc, so
After be added in three-necked flask, add p-methyl benzenesulfonic acid, be heated to 130 DEG C of condensing refluxes, have in spherical condensation tube reflux produce
It is raw, insulation reaction 7-8h.
（3）TDI is added into dissaving polymer obtained above, and p-methyl benzenesulfonic acid is added and makees catalyst, stirs
Uniformly, constant temperature successive reaction 6 hours, vacuum distillation.It must be the dissaving polymer of isocyanates to end.
（4）Melamine, and addition pair are added in the dissaving polymer for end obtained above being isocyanates
Toluenesulfonic acid makees catalyst, stirs evenly, constant temperature successive reaction 4 hours, vacuum distillation.Obtain the melamine of hyperbranched type.
（5）Hyperbranched type melamine and cyanuric acid is soluble in water that suspension is made, then in 100 DEG C of -120 DEG C of reactions
A few hours, after slurry become slit it is thick after the reaction was continued a period of time, using filter, drying, it is broken obtain hyperbranched type MCA at
Product.
（6）It is added to the 10% of hyperbranched type MCA fire retardants PA6 material gross masses obtained above, synthesis has resistance
Fire the material of performance.Sample is prepared according to standard GB/T 2406.2-2009 and measures its flame retardant property limit oxygen index.
Implementation four
(1) phthalic anhydride is accurately weighed with electronic balance, is dissolved in n,N-dimethylacetamide（DMAc）, it is placed in beaker
In, fully dissolve.Two different hydramine are added into three-necked flask, stir evenly.The phthalic anhydride fully dissolved is instilled three
In mouth flask, 3 h are reacted under room temperature, obtain AB2Monomer.
（2）Toluene is first added in above-mentioned system, weighs trimethylolpropane, so that it is fully dissolved with a small amount of DMAc, so
After be added in three-necked flask, add p-methyl benzenesulfonic acid, be heated to 130 DEG C of condensing refluxes, have in spherical condensation tube reflux produce
It is raw, insulation reaction 7-8h.
（3）TDI is added into dissaving polymer obtained above, and p-methyl benzenesulfonic acid is added and makees catalyst, stirs
Uniformly, constant temperature successive reaction 6 hours, vacuum distillation.It must be the dissaving polymer of isocyanates to end.
（4）Melamine, and addition pair are added in the dissaving polymer for end obtained above being isocyanates
Toluenesulfonic acid makees catalyst, stirs evenly, constant temperature successive reaction 4 hours, vacuum distillation.Obtain the melamine of hyperbranched type.
（5）Hyperbranched type melamine and cyanuric acid is soluble in water that suspension is made, then in 100 DEG C of -120 DEG C of reactions
A few hours, after slurry become slit it is thick after the reaction was continued a period of time, using filter, drying, it is broken obtain hyperbranched type MCA at
Product.
（6）It is added to the 12% of hyperbranched type MCA fire retardants PA6 material gross masses obtained above, synthesis has resistance
Fire the material of performance.Sample is prepared according to standard GB/T 2406.2-2009 and measures its flame retardant property limit oxygen index.
Comparison example
Prepare the PA6 materials that fire retardant is not added.Sample is prepared according to mark GB/T 2406.2-2009 and measures its flame retardant property
Limit oxygen index.
Performance test
In order to illustrate the actual effect of the present invention, be exactly below will the product that be obtained in implementation of the present invention to PA6 materials into
Row adds experiment, by measuring its oxygen index (OI), evaluates the effect of fire retardant.
Sample preparation and test are carried out to material according to GB/T 2406.2-2009.Test performance is as follows：
Table 1：Oxygen index (OI) is tested
| Project | Oxygen index (OI)/% |
| Embodiment 1 | 31 |
| Embodiment 2 | 33.5 |
| Embodiment 3 | 36 |
| Embodiment 4 | 37.5 |
| Comparison example | 29.5 |
As shown in Table 1, after adding the made hyperbranched type MCA fire retardants of the present invention, the oxygen index (OI) of PA6 materials significantly improves,
Prove that the fire retardant effect of the present invention is fine.Fire retardant of the present invention has a large amount of carbon source and nitrogen source, and has a large amount of phenyl ring,
In polymer combustion, the substance group with flame retarding function is concentrated to act synergistically, promotes flame retardant effect, traditional MCA is made to hinder
Combustion agent additive amount substantially reduces, and has saved cost.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not limited by embodiment
System, other any changes made without departing from the spirit and principles of the present invention, modification, combination, replacement, simplification should be
Equivalence replacement mode, is included within the scope of the present invention.
Claims (8)
1. a kind of hyperbranched type MCA fire retardants, it is characterized in that obtained by following steps：
1. phthalic anhydride and two different hydramine reactions generate AB2Monomer；
2. core molecule trimethylolpropane and AB2Monomer is according to 1:It is anti-that 3-45 molar ratio reactions obtain Hyperbranched Polymer with Terminal Hydroxyl
It answers；
3. being carried out to Hyperbranched Polymer with Terminal Hydroxyl terminal-modified, is blocked, obtained isocyanate-terminated hyperbranched with TDI
Polymer；
4. isocyanate-terminated dissaving polymer and melamine to be obtained by the reaction to the melamine of hyperbranched type；
5. hyperbranched type melamine and cyanuric acid is soluble in water that suspension is made, then small in 100 DEG C of -120 DEG C of stoichiometric numbers
When, after slurry become slit it is thick after the reaction was continued a period of time, using filter, drying, broken obtain the finished product of hyperbranched type MCA.
2. a kind of hyperbranched type MCA fire retardants are in the fire-retardant application for improving PA6 materials, it is characterised in that a large amount of trimerization in end
Cyanamide cyanurate generates layer of charcoal after combustion, further hinders the burning of PA6 materials.
3. application according to claim 1, it is characterised in that fire retardant of the hyperbranched type MCA fire retardants as PA6 materials
Addition content is the 6 ~ 12% of PA6 material gross masses.
4. application according to claim 1, it is characterised in that core molecule and TDI molar ratios are 1：6、1：12、1：24 or 1：
48, it is the hyperbranched polies that the dissaving polymer of isocyanates, second generation end are isocyanates to respectively obtain first generation end
Close dissaving polymer that object, third generation end are isocyanates or forth generation end be isocyanates dissaving polymer.
5. application according to claim 1 is the super of isocyanates in addition to being modified hydroxy-terminated polymer to obtain end group with TDI
Branched polymer can also use a variety of polyisocyanates.
6. application according to claim 1, it is characterised in that melamine and end are the hyperbranched polymerizations of isocyanates
Object and melamine polymerization are according to 1：12、1：24 or 1：The hyperbranched melamine of the second generation that 48 molar ratio reactions respectively obtain,
The hyperbranched melamine of the third generation and the hyperbranched melamine of forth generation.
7. application according to claim 1, it is characterised in that hyperbranched type melamine and cyanuric acid are according to 1：12、1：24
Or 1：Hyperbranched type MCA fire retardants of the second generation that 48 molar ratio reactions respectively obtain, the hyperbranched type MCA fire retardants of the third generation and
Four generations hyperbranched type MCA fire retardants.
8. application according to claim 1, it is characterized in that the AB of the dissaving polymer2Monomer is by phthalic acid
Acid anhydride and two different hydramine are according to molar ratio 1：1 synthesis.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484190A (en) * | 2019-09-05 | 2019-11-22 | 山西省应用化学研究所(有限公司) | Caravan vehicle body solvent-free single-component moisture cure urethanes adhesive and preparation method thereof |
| CN111234157A (en) * | 2020-03-09 | 2020-06-05 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262680A (en) * | 2014-10-15 | 2015-01-07 | 济南大学 | Hyperbranched intumescent flame retardant and preparation method thereof |
| CN106380595A (en) * | 2016-09-06 | 2017-02-08 | 济南大学 | Preparation method of hyperbranched flame retardant and application of hyperbranched flame retardant in polyurethane |
| CN107099131A (en) * | 2017-04-07 | 2017-08-29 | 北京理工大学 | A kind of hyperbranched common modified chain extension extinguishing waterborn polyurethane of blending soft and hard segments |
| CN107540847A (en) * | 2017-07-27 | 2018-01-05 | 济南大学 | The preparation method of hyperbranched fire retardant and the application in wood-based plate |
-
2018
- 2018-03-19 CN CN201810222755.4A patent/CN108440764A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262680A (en) * | 2014-10-15 | 2015-01-07 | 济南大学 | Hyperbranched intumescent flame retardant and preparation method thereof |
| CN106380595A (en) * | 2016-09-06 | 2017-02-08 | 济南大学 | Preparation method of hyperbranched flame retardant and application of hyperbranched flame retardant in polyurethane |
| CN107099131A (en) * | 2017-04-07 | 2017-08-29 | 北京理工大学 | A kind of hyperbranched common modified chain extension extinguishing waterborn polyurethane of blending soft and hard segments |
| CN107540847A (en) * | 2017-07-27 | 2018-01-05 | 济南大学 | The preparation method of hyperbranched fire retardant and the application in wood-based plate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484190A (en) * | 2019-09-05 | 2019-11-22 | 山西省应用化学研究所(有限公司) | Caravan vehicle body solvent-free single-component moisture cure urethanes adhesive and preparation method thereof |
| CN111234157A (en) * | 2020-03-09 | 2020-06-05 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
| CN111234157B (en) * | 2020-03-09 | 2021-10-19 | 江苏科技大学 | Reactive extrusion preparation method of flame-retardant hyperbranched polyamide 6 elastomer |
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