CN110105306A - A kind of modified piperazine pyrophosphate and its preparation method and application - Google Patents
A kind of modified piperazine pyrophosphate and its preparation method and application Download PDFInfo
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- CN110105306A CN110105306A CN201910304018.3A CN201910304018A CN110105306A CN 110105306 A CN110105306 A CN 110105306A CN 201910304018 A CN201910304018 A CN 201910304018A CN 110105306 A CN110105306 A CN 110105306A
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- Prior art keywords
- piperazine pyrophosphate
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- piperazine
- pyrophosphate
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- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical class C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003063 flame retardant Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229920005629 polypropylene homopolymer Polymers 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims 2
- 230000004048 modification Effects 0.000 claims 2
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000000088 plastic resin Substances 0.000 abstract description 4
- 230000000979 retarding effect Effects 0.000 abstract description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229960005141 piperazine Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical class CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000003938 benzyl alcohols Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- 229960001954 piperazine phosphate Drugs 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- 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
Abstract
The invention discloses a kind of modified piperazine pyrophosphates and its preparation method and application.The preparation method is that: under conditions of protective gas, into reaction kettle, piperazine pyrophosphate, small molecular alcohol and catalyst is added, is stirred under the conditions of 180-260 DEG C, after insulation reaction 1-5 hours, vacuum distillation removing moisture is to get modified piperazine pyrophosphate.By it with homopolypropylene with mass ratio (20-24): the ratio of (76-80) mixes mixing, and the flame retardant rating of products therefrom reaches UL94 (1.6mm) V-0 grade.The present invention is modified by carrying out molecular structure to piperazine pyrophosphate, is introduced non-polar component into piperazine pyrophosphate molecule, is increased its compatibility between plastic resin with this, so as to improve its dispersion performance in the plastic, improves flame retarding efficiency.
Description
Technical field
The present invention relates to a kind of preparation method and application of modified piperazine pyrophosphate, and in particular to a kind of to utilize small molecular alcohol
The preparation method of modified piperazine pyrophosphate.
Background technique
Halogen-free flame retardants because of the features such as its is more environmentally-friendly, is not likely to produce poison gas in combustion process, and flame retarding efficiency is high,
Application field increasingly replaces halogenated flame retardant to become the primary selection that fire proofing is formulated.On international market, European Union, Japan
Equal areas (country) is especially stringent to the requirement that electronic product is non-halogen.Basis of the ammonium polyphosphate (APP) as halogen-free flame retardants
In the past few decades as the core component of halogen-free flame retardants, play the role of to security against fire indelible.However, with
Science and technology progress, the common people to building live, product use the safe meaning continuous promotion, the initiative of fire proofing is proposed
Increasingly higher demands.And APP is easily precipitated, easy to migrate, flame retarding efficiency is low, easy point of processing as previous generation product because it exists
The problems such as solution, becomes the technical requirements for being increasingly unable to satisfy advanced industry.For this purpose, piperazine pyrophosphate is made as APP is replaced
It is suggested out for the initiative core of halogen-free flame retardants.
Currently, the preparation method and technique of piperazine pyrophosphate in the prior art, comparative maturity.Such as Chinese patent
A kind of method preparing piperazine pyrophosphate using piperazine phosphate dehydrating condensation, Chinese patent disclosed in 201110124271.4
A kind of method etc. that piperazine pyrophosphate is prepared using ammonium dihydrogen phosphate and piperazine disclosed in 201610364678.7.
However, in the specific use process of piperazine pyrophosphate, due to its as inorganic particle and organic plastic resin it
Between there are still biggish nature difference, cause its additive amount excessively high, otherwise be easy be precipitated, influence product appearance；Or it is
Its dispersion is promoted to need that its grain diameter is prepared into minimum (less than 10 microns) by post-processing, and this causes processing
It is extremely difficult in the process only to reach substantially finely dispersed purpose by way of mixing.The two distinct issues result in pyrophosphoric acid
Piperazine is unable to the addition of large scale and can not be applied in the product piece more demanding to appearance.
Summary of the invention
Problem to be solved by this invention is: how to improve the compatibility between piperazine pyrophosphate and plastic resin, reaches
The purpose for promoting dispersion, improving flame retarding efficiency.
To solve the above-mentioned problems, the present invention provides following technical schemes:
A kind of preparation method of modified piperazine pyrophosphate, which is characterized in that under conditions of protective gas, to reaction kettle
In, piperazine pyrophosphate, small molecular alcohol and catalyst is added, stirs under the conditions of 180-260 DEG C, after insulation reaction 1-5 hours, subtracts
Pressure distillation removing moisture is to get modified piperazine pyrophosphate.
Preferably, the protective gas is using nitrogen (purity is greater than 99.9%) or argon gas (purity is greater than 99.9%).
Preferably, the boiling point of the small molecular alcohol is higher than 180 DEG C.
Preferably, the small molecular alcohol uses the mixed of any one or a few in benzyl alcohol, benzyl carbinol and pentaerythrite
Close object.
Preferably, the catalyst be zinc acetate, manganese acetate, sodium acetate, potassium acetate, cobalt acetate, lithium acetate, acetic anhydride,
Any one or a few mixture in phthalic anhydride, antimony oxide, stannous acetate and calcium acetate；The catalyst
Additive amount be all reactant gross mass 0.1-0.3wt%.
Preferably, the molar ratio of the piperazine pyrophosphate and small molecular alcohol is 1:1.0-1.5.
Preferably, the temperature 60 C of the vacuum distillation.
The present invention also provides modified piperazine pyrophosphates made from a kind of preparation method of above-mentioned modified piperazine pyrophosphate.
Preferably, the chemical formula of the modified piperazine pyrophosphate are as follows:
Wherein, R is
The present invention also provides a kind of applications of above-mentioned modified piperazine pyrophosphate, which is characterized in that by itself and homopolymerization poly- third
Alkene is with mass ratio (20-24): the ratio of (76-80) mixes mixing, and the flame retardant rating of products therefrom reaches UL94 (1.6mm) V-0
Grade.
The present invention is modified by carrying out molecular structure to piperazine pyrophosphate, and nonpolar group is introduced into piperazine pyrophosphate molecule
Point, its compatibility between plastic resin is increased with this, so as to improve its dispersion performance in the plastic, improves fire-retardant effect
Rate.
Specific embodiment
In order to make the present invention more obvious and understandable, it is hereby described in detail below with preferred embodiment.
Embodiment 1
In the 5L glass reaction kettle for being mounted with blender, thermometer and exhaust tube, be added 1.08kg piperazine pyrophosphate and
Atmosphere in reaction kettle is replaced into argon gas (purity is greater than 99.99%), is sufficiently stirred by 0.65kg benzyl carbinol and 3.46g lithium acetate
After mixing, reaction kettle is warming up to 210 DEG C and constant temperature is kept to stir 2h；In reaction process, generation water is carried out due to esterification
Point, material gradually becomes viscous；After reacting 2h, exhaust tube is opened, using vacuum suction mode, the moisture that reaction generates is taken off
Out, obtain it is powdered modified after piperazine pyrophosphate powder, yield 92.5%.
Embodiment 2
In the 5L glass reaction kettle for being mounted with blender, thermometer and exhaust tube, be added 1.08kg piperazine pyrophosphate and
Atmosphere in reaction kettle is replaced into argon gas (purity is greater than 99.99%), is sufficiently stirred by 0.70kg pentaerythrite and 8.9g acetic anhydride
After mixing, reaction kettle is warming up to 190 DEG C and constant temperature is kept to stir 1.5h；In reaction process, generate due to esterification
Moisture, material gradually become viscous；After reacting 1.5h, exhaust tube is opened, using vacuum suction mode, the moisture that reaction is generated
Abjection, obtain it is powdered modified after piperazine pyrophosphate powder, yield 92.1%.
Embodiment 3
In the 5L glass reaction kettle for being mounted with blender, thermometer and exhaust tube, be added 1.08kg piperazine pyrophosphate and
Atmosphere in reaction kettle is replaced into argon gas (purity is greater than 99.99%), through filling by 0.54kg benzyl alcohol and 8.1g phthalic anhydride
After dividing stirring, reaction kettle is warming up to 190 DEG C and constant temperature is kept to stir 1.5h；In reaction process, due to the progress of esterification
Moisture is generated, material gradually becomes viscous；After reacting 1.5h, exhaust tube is opened, using vacuum suction mode, reaction is generated
Moisture abjection, obtain it is powdered modified after piperazine pyrophosphate powder, yield 91.8%.
Embodiment 4
In the 10L vacuum kneader for being mounted with blender, thermometer and exhaust tube, be added 2.16kg piperazine pyrophosphate and
Atmosphere in kneader is replaced into nitrogen (purity is greater than 99.99%), warp by 1.08kg benzyl alcohol and 16.2g phthalic anhydride
After mediating uniformly, reaction kettle is warming up to 220 DEG C and continues to mediate 2.5h；In reaction process, produce due to esterification
Unboiled water point, material gradually becomes viscous；After reacting 2.5h, kneader vacuum port is opened, using vacuum suction mode, reaction is produced
Raw moisture abjection, obtain it is powdered modified after piperazine pyrophosphate powder, yield 91.6%.
Embodiment 5
24 parts by weight benzyl alcohols are modified piperazine pyrophosphate and 86 parts by weight homopolypropylene (T300, Maoming Petrochemical),
After five minutes, 190 DEG C of moulding press are pressed into 1.6mm thin slice for 180 DEG C of mixings in mixer.
UL94 1.6mm standard batten is prepared by sampling machine in above-mentioned thin slice, it is quasi- in the enterprising rower of burning series instrument
Test.After tested, sample flame retardant rating are as follows: UL94 1.6mm v-0 grade, tensile strength 35.3MPa, elongation at break
90.7%.
Embodiment 6
24 Weight parts Phenylethanols are modified piperazine pyrophosphate and 86 parts by weight homopolypropylene (T300, Maoming Petrochemical),
After five minutes, 190 DEG C of moulding press are pressed into 1.6mm thin slice for 180 DEG C of mixings in mixer.
UL94 1.6mm standard batten is prepared by sampling machine in above-mentioned thin slice, it is quasi- in the enterprising rower of burning series instrument
Test.After tested, sample flame retardant rating are as follows: UL94 1.6mm v-0 grade, tensile strength 33.5MPa, elongation at break
150.7%.
Comparative example
By the unmodified piperazine pyrophosphate of 24 parts by weight and 86 parts by weight homopolypropylene (T300, Maoming Petrochemical), in mixing
After five minutes, 190 DEG C of moulding press are pressed into 1.6mm thin slice for 180 DEG C of mixings in machine.
UL94 1.6mm standard batten is prepared by sampling machine in above-mentioned thin slice, it is quasi- in the enterprising rower of burning series instrument
Test.After tested, sample flame retardant rating are as follows: off grade, tensile strength 29.1MPa, elongation at break 40.5%.
Claims (10)
1. a kind of preparation method of modified piperazine pyrophosphate, which is characterized in that under conditions of protective gas, into reaction kettle,
Piperazine pyrophosphate, small molecular alcohol and catalyst is added, is stirred under the conditions of 180-260 DEG C, after insulation reaction 1-5 hours, decompression
Distillation removing moisture is to get modified piperazine pyrophosphate.
2. the preparation method of modified piperazine pyrophosphate as described in claim 1, which is characterized in that the protective gas uses nitrogen
Gas or argon gas.
3. the preparation method of modified piperazine pyrophosphate as described in claim 1, which is characterized in that the boiling point of the small molecular alcohol
Higher than 180 DEG C.
4. the preparation method of modified piperazine pyrophosphate as claimed in claim 1 or 2, which is characterized in that the small molecular alcohol is adopted
With any one or a few the mixture in benzyl alcohol, benzyl carbinol and pentaerythrite.
5. the preparation method of modified piperazine pyrophosphate as described in claim 1, which is characterized in that the catalyst is acetic acid
Zinc, manganese acetate, sodium acetate, potassium acetate, cobalt acetate, lithium acetate, acetic anhydride, phthalic anhydride, antimony oxide, stannous acetate
With any one or a few the mixture in calcium acetate；The additive amount of the catalyst is the 0.1- of all reactant gross mass
0.3wt%.
6. the preparation method of modified piperazine pyrophosphate as described in claim 1, which is characterized in that the piperazine pyrophosphate with it is small
The molar ratio of molecule alcohol is 1:1.0-1.5.
7. the preparation method of modified piperazine pyrophosphate as described in claim 1, which is characterized in that the temperature of the vacuum distillation
60℃。
8. modified pyrophosphoric acid piperazine made from a kind of preparation method of modification piperazine pyrophosphate described in claim 1-7 any one
Piperazine.
9. modified piperazine pyrophosphate as claimed in claim 8, which is characterized in that the chemical formula of the modified piperazine pyrophosphate
Are as follows:
Wherein, R is
10. the application of modification piperazine pyrophosphate described in a kind of claim 8 or 9, which is characterized in that by itself and homopolypropylene
With mass ratio (20-24): the ratio of (76-80) mixes mixing, and the flame retardant rating of products therefrom reaches UL94 (1.6mm) V-0 etc.
Grade.
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| Application Number | Priority Date | Filing Date | Title |
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| CN110105306A true CN110105306A (en) | 2019-08-09 |
Family
ID=67485501
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|---|---|---|---|---|
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| JP2017008221A (en) * | 2015-06-23 | 2017-01-12 | 株式会社Adeka | Fire retardant synthetic resin composition |
-
2019
- 2019-04-16 CN CN201910304018.3A patent/CN110105306A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343387A (en) * | 2007-07-12 | 2009-01-14 | 上海化工研究院 | Halogen-free water resistant expansion type phosphor nitrogen combustion inhibitor for polyolefin and preparation thereof |
| JP2017008221A (en) * | 2015-06-23 | 2017-01-12 | 株式会社Adeka | Fire retardant synthetic resin composition |
Non-Patent Citations (1)
| Title |
|---|
| LIU, HAICHAO 等: "An efficient and convenient strategy toward fire safety and water resistance of polypropylene composites through design and synthesis of a novel mono-component intumescent flame retardant", 《POLYMERS FOR ADVANCED TECHNOLOGIES》 * |
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