CN107266890A - A kind of unsaturated polyester resin halogen-free flame retardants and its preparation method and application - Google Patents

A kind of unsaturated polyester resin halogen-free flame retardants and its preparation method and application Download PDF

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CN107266890A
CN107266890A CN201710562915.5A CN201710562915A CN107266890A CN 107266890 A CN107266890 A CN 107266890A CN 201710562915 A CN201710562915 A CN 201710562915A CN 107266890 A CN107266890 A CN 107266890A
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polyester resin
unsaturated polyester
parts
flame retardants
halogen
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徐亮
肖学文
侯进京
王艳辉
周生刚
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JINAN TAIXING FINE CHEMICAL CO Ltd
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JINAN TAIXING FINE CHEMICAL CO Ltd
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a kind of unsaturated polyester resin halogen-free flame retardants and preparation method thereof, the fire retardant is mixed by phosphor nitrogen combustion inhibitor, containing boron fire retardant preservative, metal hydroxides, metal oxide, carbon forming agent, modifying agent by certain technique.The present invention is Halogen, environment-friendly products, avoid the secondary hazards that halogen containing flame-retardant produces pernicious gas and smog and caused, the unsaturated polyester resin of different model can be widely used in, the addition 15~35% in unsaturated polyester resin product, oxygen index (OI) stably reaches more than 30%, and flame retarding efficiency is high.Preparation technology of the present invention is simple, and the compatibility with unsaturated polyester resin is good, and other performances of product are not influenceed, it is to avoid the problems such as sedimentation, influence solidification, intensity decline.With the features such as dispersive property is excellent, performance is stable, the product surface of preparation is attractive in appearance, defect is few.

Description

A kind of unsaturated polyester resin halogen-free flame retardants and its preparation method and application
Technical field
The present invention relates to a kind of fire retardant, specifically a kind of Halogen highly effective flame-retardant being applied in unsaturated polyester resin Agent and its preparation method and application, belongs to technical field of flame retardant.
Background technology
Unsaturated polyester resin (UPR) is the polycondensation product of unsaturated dibasic acid (or acid anhydrides) and polyalcohol, generally with benzene Ethene is made crosslinking agent and solidified under heating or normal temperature condition, can be made into a variety of section bars, because production technology is easy, raw material is easy to get, While resistant to chemical etching, mechanical property, excellent electrical properties, it is most important that can be so that normal temperature and pressure solidifies and has good technique Performance, thus can be widely used in as the glass fiber reinforced plastics composite material product such as structure, anti-corrosion, insulation building, shipbuilding, auto industry, The fields such as chemical industry equipment, light industrial products and sports goods.UPR consumptions account for 85-90%, fiberglass in thermosetting resin Resin with the most use in composite product production.But unsaturated polyester resin product oxygen index (OI) is low, product is inflammable, Chang You Fire occurs, and causes immeasurable loss to life and property, therefore unsaturated polyester resin product is carried out into flame retardant treatment It is more aobvious urgent.
The halogen-free flame retardants species of current unsaturated polyester resin is less, and in the market is more with halogen sb system fire retardant and liquid Based on phosphate ester flame retardants, wherein halogen sb system fire retardant produces a large amount of pernicious gases and smog during fire-retardant, gives people Life and property safety cause secondary hazards, do not meet《RoHS is instructed》；And the fire-retardant effect of liquid phosphoric acid esters fire retardant Rate is low, and addition is big, generally requires to use cooperatively with other fire retardants to strengthen flame retardant effect, increases application cost, and And unsaturated polyester resin there is also compatibility it is poor, layering, separate out the problems such as so that influence product flame retardant effect and Normally use.
The content of the invention
It is an object of the present invention to provide a kind of unsaturated polyester resin halogen-free flame retardants, by the raw material of following parts by weight It is made：20~100 parts of phosphor nitrogen combustion inhibitor, containing 1~10 part of boron fire retardant preservative, 5~40 parts of metal hydroxides, metal oxide 1~5 Part, 5~40 parts of carbon forming agent, 0.1~2 part of modifying agent.
Described phosphorus-nitrogen containing flame retardant is APP, melamine phosphate, melamine pyrophosphate, hypo-aluminum orthophosphate, phosphoric acid hydrogen One kind in two ammoniums, ammonium dihydrogen phosphate, triammonium phosphate, melamine, melamine cyanurate, urea, ammonium sulfate, ammonium chloride Or two kinds and combination of the above.
It is described containing boron fire retardant preservative be one or both of boric acid, borax, Firebrake ZB, barium metaborate, ammonium pentaborate and Combination of the above.
Described metal hydroxides is the combination of one or both of magnesium hydroxide, aluminium hydroxide.
Described metal oxide is one or both of magnesia, aluminum oxide, zinc oxide, calcium oxide and above group Close.
Described carbon forming agent is starch, sorbierite, pentaerythrite, bipentaerythrite, tripentaerythritol, ethylene glycol, the third three Alcohol, poly- p-phenylene ethene diamine, the one or two and combination of the above of poly- 2- ethylenediamines base -4- phenoxy group -1,3,5- triazines.
Described modifying agent is stearic acid, titanate esters, silane resin acceptor kh-550, KH-560, KH-570, KH-171, KH- 172nd, one or both of KH-792, DL602 are combined.
It is a further object to provide a kind of preparation method of unsaturated polyester resin halogen-free flame retardants, technical side Case is as follows：
1) phosphor nitrogen combustion inhibitor is added and 10~60min is mixed in high-speed mixer, be warming up to 40~120 DEG C, added and be modified Agent, 5~60min of mixed at high speed, discharging, sieving after material cooling；
2) by metal hydroxides, metal oxide, added containing boron fire retardant preservative and carbon forming agent in low speed mixer and mix 10 ~60min, discharging, sieving；
3) take step 1) with step 2) obtained by material, add low speed mixer in mix 20~60min, discharging, sieving, Packaging, is produced.
It is also another object of the present invention to provide application of the described fire retardant in unsaturated polyester resin product.
The invention has the advantages that：
1st, the present invention is Halogen, environment-friendly products, meets external, Environmental Protection in China regulation, it is to avoid as halogen containing flame-retardant is in resistance The secondary hazards for producing pernicious gas and smog during combustion and causing, with positive society, safety benefit.
2nd, the present invention is a kind of efficient flame-retarding agent, the unsaturated polyester resin of different model can be widely used in, not Addition 15~35% in saturated polyester resin product, oxygen index (OI) stably reaches more than 30%, and flame retarding efficiency is high.
3rd, preparation technology of the present invention is simple, and cost of material is low, and price advantage is obvious.
4th, the present invention is powder, and by modification, the compatibility with unsaturated polyester resin is good, poly- applied to unsaturation There is the features such as good dispersion, performance are stable, it is to avoid occur during using liquid phosphoric acid esters fire retardant when in ester naval stores Layering, separate out the problems such as, so as to ensure that flame retardant effect is effective for a long time.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of unsaturated polyester resin halogen-free flame retardants, is made up of the raw material of following weight parts：45 parts of melamine pyrophosphate, 20 parts of melamine cyanurate, 10 parts of triammonium phosphate, 3 parts of Firebrake ZB, 33 parts of aluminium hydroxide, 3 parts of zinc oxide, bipentaerythrite 15 parts, 1 part of KH-560.
Preparation method：
1) raw material is weighed according to above-mentioned parts by weight, melamine pyrophosphate, melamine cyanurate, triammonium phosphate is added 20min is mixed in high-speed mixer, 50 DEG C are warming up to, KH-560, mixed at high speed 5min is added, discharging, sieving after material cooling；
2) Firebrake ZB, aluminium hydroxide, zinc oxide and bipentaerythrite are weighed according to above-mentioned parts by weight, adds low speed mixer Middle mixing 15min, discharging, sieving；
3) take step 1) with step 2) obtained by material, add low speed mixer in mix 25min, discharging, sieving, bag Dress, is produced.
Embodiment 2
A kind of unsaturated polyester resin halogen-free flame retardants, is made up of the raw material of following weight parts：45 parts of APP, trimerization 20 parts of cyanamide cyanurate, 5 parts of Firebrake ZB, 10 parts of aluminium hydroxide, 3.5 parts of magnesia, 2 parts of calcium oxide, 21 parts of pentaerythrite, 0.5 part of KH-172.
Preparation method：
1) raw material is weighed according to above-mentioned parts by weight, APP, melamine cyanurate is added in high-speed mixer 30min is mixed, 90 DEG C are warming up to, KH-172, mixed at high speed 20min is added, discharging, sieving after material cooling；
2) Firebrake ZB, aluminium hydroxide, magnesia, calcium oxide and pentaerythrite are weighed according to above-mentioned parts by weight, adds low speed 20min, discharging, sieving are mixed in mixer；
3) take step 1) with step 2) obtained by material, add low speed mixer in mix 25min, discharging, sieving, bag Dress, is produced.
Embodiment 3
A kind of unsaturated polyester resin halogen-free flame retardants, is made up of the raw material of following weight parts：25 parts of hypo-aluminum orthophosphate, trimerization 20 parts of cyanamide cyanurate, 5 parts of ammonium dihydrogen phosphate, 2 parts of borax, 10 parts of aluminium hydroxide, 10 parts of magnesium hydroxide, 4 parts of calcium oxide, season Penta 25 parts of tetrol, 3 parts of starch, 1 part of KH-570.
Preparation method：
1) raw material is weighed according to above-mentioned parts by weight, hypo-aluminum orthophosphate, melamine cyanurate, ammonium dihydrogen phosphate is added high 25min is mixed in fast mixer, 40 DEG C are warming up to, KH-570, mixed at high speed 50min is added, discharging, sieving after material cooling；
2) borax, aluminium hydroxide, magnesium hydroxide, calcium oxide, pentaerythrite and starch are weighed according to above-mentioned parts by weight, added 35min, discharging, sieving are mixed in low speed mixer；
3) take step 1) with step 2) obtained by material, add low speed mixer in mix 20min, discharging, sieving, bag Dress, is produced.
Embodiment 4
A kind of unsaturated polyester resin halogen-free flame retardants, is made up of the raw material of following weight parts：25 parts of APP, sulfuric acid 25 parts of ammonium, 5 parts of melamine, 7 parts of Firebrake ZB, 30 parts of aluminium hydroxide, 2.5 parts of calcium oxide, 10 parts of bipentaerythrite, KH-550 0.5 part.
Preparation method：
1) raw material is weighed according to above-mentioned parts by weight, APP, ammonium sulfate, melamine is added in high-speed mixer and mixed 25min is closed, 80 DEG C are warming up to, KH-550, mixed at high speed 30min is added, discharging, sieving after material cooling；
2) calcium oxide, aluminium hydroxide, Firebrake ZB and bipentaerythrite are weighed according to above-mentioned parts by weight, adds low speed mixer Middle mixing 20min, discharging, sieving；
3) take step 1) with step 2) obtained by material, add low speed mixer in mix 25min, discharging, sieving, bag Dress, is produced.
Experimental example
It is unsaturated poly- applied to 191 using unsaturated polyester resin halogen-free flame retardants made from the above embodiment of the present invention In ester resin, each group distribution ratio such as table 1, wherein reference substance 1 are the product without fire retardant, and reference substance 2 uses certain commercially available public affairs DMMP products are taken charge of, sample 1~4 uses fire retardant made from the embodiment of the present application 1~4 respectively.Each component adds number and fire-retardant Performance (oxygen index (OI)) test such as table 1：
The plane skylight fire block articles performance test of table 1
Component Reference substance 1 Reference substance 2 Sample 1 Sample 2 Sample 3 Sample 4
Resin 100 parts 100 parts 100 parts 100 parts 100 parts 100 parts
Glass 20 parts 20 parts 20 parts 20 parts 20 parts 20 parts
Fire retardant 0 part 30 parts 30 parts 30 parts 30 parts 30 parts
Curing agent 2 parts 2 parts 2 parts 2 parts 2 parts 2 parts
Accelerator 2 parts 2 parts 2 parts 2 parts 2 parts 2 parts
Products thickness 1.5mm 1.5mm 1.5mm 1.5mm 1.5mm 1.5mm
Oxygen index (OI) 19.3% 28.6% 32.4% 32.7% 33.1% 32.3%
As it can be seen from table 1 under identical addition, the product prepared using the agent of the embodiment of the present application 1-4 obtained flame-retardants Oxygen index value is all higher than 32%, hence it is evident that better than reference substance, and meets in GB50222 code for fire prevention design of interior decoration of buildings B1 grades The index of oxygen index (OI).
The description of the foregoing specific illustrative embodiment to the application be in order to illustrate and illustration purpose.These descriptions It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to above-mentioned teaching, can be much changed And change.The purpose of selecting and describing the exemplary embodiment is that explaining that the certain principles and its reality of the present invention should With so that those skilled in the art can realize and using the present invention a variety of exemplaries and A variety of selections and change.

Claims (9)

1. a kind of unsaturated polyester resin halogen-free flame retardants, it is characterised in that be made up of the raw material of following parts by weight：Phosphorus nitrogen is fire-retardant 20~100 parts of agent, containing 1~10 part of boron fire retardant preservative, 5~40 parts of metal hydroxides, 1~5 part of metal oxide, carbon forming agent 5~ 40 parts, 0.1~2 part of modifying agent.
2. unsaturated polyester resin halogen-free flame retardants according to claim 1, it is characterised in that described phosphor nitrogen combustion inhibitor For APP, melamine phosphate, melamine pyrophosphate, hypo-aluminum orthophosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, three One or both of poly cyanamid, melamine cyanurate, urea, ammonium sulfate, ammonium chloride and combination of the above.
3. unsaturated polyester resin halogen-free flame retardants according to claim 1, it is characterised in that described contains boron fire retardant preservative For one or both of boric acid, borax, Firebrake ZB, barium metaborate, ammonium pentaborate and combination of the above.
4. unsaturated polyester resin halogen-free flame retardants according to claim 1, it is characterised in that described metal hydroxide Thing is the combination of one or both of magnesium hydroxide, aluminium hydroxide.
5. unsaturated polyester resin halogen-free flame retardants according to claim 1, it is characterised in that described metal oxide For one or both of magnesia, aluminum oxide, zinc oxide, calcium oxide and combination of the above.
6. unsaturated polyester resin halogen-free flame retardants according to claim 1, it is characterised in that described carbon forming agent is shallow lake It is powder, sorbierite, pentaerythrite, bipentaerythrite, tripentaerythritol, ethylene glycol, glycerine, poly- p-phenylene ethene diamine, poly- The one or two and combination of the above of 2- ethylenediamine base -4- phenoxy group -1,3,5- triazines.
7. unsaturated polyester resin halogen-free flame retardants according to claim 1, it is characterised in that described modifying agent is hard One kind in resin acid, titanate esters, silane resin acceptor kh-550, KH-560, KH-570, KH-171, KH-172, KH-792, DL602 Or two kinds of combinations.
8. the preparation method of the unsaturated polyester resin halogen-free flame retardants described in claim any one of 1-7, it is characterised in that step It is rapid as follows：
1) phosphor nitrogen combustion inhibitor is added and 10~60min is mixed in high-speed mixer, be warming up to 40~120 DEG C, add modifying agent, it is high Speed 5~60min of mixing, discharging, sieving after material cooling；
2) added by metal hydroxides, metal oxide, containing boron fire retardant preservative and carbon forming agent mixing 10 in low speed mixer~ 60min, discharging, sieving；
3) take step 1) with step 2) obtained by material, add low speed mixer in mix 20~60min, discharging, sieving, bag Dress, is produced.
9. application of the fire retardant described in claim any one of 1-7 in unsaturated polyester resin product.
CN201710562915.5A 2017-07-11 2017-07-11 A kind of unsaturated polyester resin halogen-free flame retardants and its preparation method and application Pending CN107266890A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109294194A (en) * 2018-09-14 2019-02-01 南京工业大学 High-flame-retardancy unsaturated polyester composite material and preparation method thereof
CN109503885A (en) * 2018-12-03 2019-03-22 济南泰星精细化工有限公司 A kind of epoxy resin halogen-free flame retardants and its preparation method and application
CN109837756A (en) * 2019-02-25 2019-06-04 浙江久大纺织科技有限公司 A kind of preparation method of flame retardant type flocking yarn
CN111040249A (en) * 2019-12-27 2020-04-21 山东柯帷博伟耐火材料有限公司 Rubber-plastic flame-retardant additive and rubber-plastic material containing same
CN112852134A (en) * 2021-01-18 2021-05-28 南京经略复合材料有限公司 Additive flame-retardant unsaturated polyester resin and preparation method thereof
CN113321850A (en) * 2021-06-21 2021-08-31 山东泰星新材料股份有限公司 Ethylene-vinyl acetate halogen-free flame retardant and preparation method thereof
CN113861507A (en) * 2021-06-25 2021-12-31 山东泰星新材料股份有限公司 B1-grade wood-plastic halogen-free flame retardant and preparation method and application thereof
CN114350025A (en) * 2022-01-10 2022-04-15 复旦大学 High-char-formation halogen-free composite intumescent flame retardant and flame-retardant polystyrene resin

Citations (4)

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CN109503885A (en) * 2018-12-03 2019-03-22 济南泰星精细化工有限公司 A kind of epoxy resin halogen-free flame retardants and its preparation method and application
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CN114350025B (en) * 2022-01-10 2023-08-18 复旦大学 High-char-forming halogen-free composite intumescent flame retardant and flame-retardant polystyrene resin

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Application publication date: 20171020