CN106117445A - A kind of preparation method of low odor polypropylene grafted maleic anhydride - Google Patents
A kind of preparation method of low odor polypropylene grafted maleic anhydride Download PDFInfo
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- CN106117445A CN106117445A CN201610609134.2A CN201610609134A CN106117445A CN 106117445 A CN106117445 A CN 106117445A CN 201610609134 A CN201610609134 A CN 201610609134A CN 106117445 A CN106117445 A CN 106117445A
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- Prior art keywords
- maleic anhydride
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- polypropylene
- low odor
- grafted maleic
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 66
- -1 polypropylene Polymers 0.000 title claims abstract description 60
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 230000002159 abnormal effect Effects 0.000 abstract description 10
- 230000035943 smell Effects 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- AEUZJPHUNWZRCJ-UHFFFAOYSA-N 1-butyl-2-propan-2-ylbenzene Chemical compound CCCCC1=CC=CC=C1C(C)C AEUZJPHUNWZRCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- RJZNFXWQRHAVBP-UHFFFAOYSA-I aluminum;magnesium;pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Al+3] RJZNFXWQRHAVBP-UHFFFAOYSA-I 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses the preparation method of a kind of low odor polypropylene grafted maleic anhydride, the method in two steps: the first step, co-monomer styrene is reacted with polypropylene under the effect of initiator, then utilize evacuation by system small molecular weight impurity remove；Second step: be subsequently adding graft phenylethene generation graft reaction on maleic anhydride and initiator, with polypropylene, finally utilizes evacuation to remove small molecular weight impurity.Utilizing the method can obtain the promoting agent for graft copolymerization of polypropylene with maleic anhydride of low abnormal smells from the patient, and percent grafting is high, preparation cost is low, economic and environment-friendly.
Description
Technical field:
The present invention relates to technical field of polypropylene, be specifically related to a kind of low odor polypropylene grafted maleic anhydride
Preparation method.
Background technology:
Polypropylene grafted maleic anhydride can be used for the filled composite materials such as glass, Pulvis Talci, calcium carbonate, aluminium hydroxide (magnesium)
Material, it act as promoting polar material and non-polar material cementability and the bridge of the compatibility, improves matrix and filler interface
The compatibility and cementability, thus it is greatly improved mechanical property and the heat resist performance of goods.
Polypropylene grafted maleic anhydride preparation method has solution graft copolymerization, fusion-grafting, solid phase grafting and Suspension Graft at present.
In actual applications, fusion-grafting method is a kind of simple to operate, and cost less investment is suitable for the preparation method of industrialized production.
The percent grafting of polypropylene grafted maleic anhydride is relevant with the addition of maleic anhydride, and percent grafting adds along with maleic anhydride
Enter the increase of amount and increase.But it is to increase maleic anhydride consumption and can cause the abnormal smells from the patient of grafted material relatively greatly, so that finally applying system
The abnormal smells from the patient of product is the biggest so that the field application high at odor requirements such as automotive trims is very limited.
In the system of maleic anhydride melt grafting PP, due to maleic anhydride symmetrical configuration, reactivity is relatively low.To have confession
In the monomer styrene addition system of electronic capability, the electric charge in maleic anhydride double bond can be made to produce asymmetric, and make its key
There is the feature of radical anion, thus improve the activity of the reaction of maleic anhydride, improve percent grafting.The most cinnamic add
Enter to suppress PP molecular radical generation chain-scission degradation, thus keep the molecular weight of PP graft.
Presently disclosed patent CN104804143A (preparation method of a kind of maleic anhydride inoculated polypropylene) and
In CN103772612A (preparation method of a kind of maleic anhydride inoculated polypropylene), utilize dual-screw-stem machine, by maleic anhydride, benzene second
Alkene, initiator are by side feeding or be blended and add reaction in screw rod in the lump because styrene under initiator effect easily with
Maleic anhydride monomer reacts generation by-product, causes percent grafting relatively low, and impurity is more, uses two-step method effectively to subtract
Few by-product produces, and maleic anhydride and styrene utilization rate are high, and product odour is compared relatively low.
Chinese patent (CN201510448574.X) discloses the polypropylene grafted maleic acid of a kind of high percent grafting, low abnormal smells from the patient
The preparation method of acid anhydride, the method adds the Petropols that 1-50% contains double bond in system, and adds auxiliary monomer styrene,
Under the effect of initiator, temperature controls at 170-230 DEG C, with maleic anhydride modified composite polypropylene and Petropols,
Then evacuation is utilized to be removed by unreacted impurity in system.Although the method can obtain the polypropylene grafted of high percent grafting
Maleic anhydride, but its maleic anhydride addition is more, and add additive Petropols, substantially increase preparation cost.
Summary of the invention:
It is an object of the invention to provide the preparation method of a kind of low odor polypropylene grafted maleic anhydride, the method prepares
Polypropylene grafted maleic anhydride abnormal smells from the patient is low, and percent grafting is high, and styrene, maleic anhydride consumption are few, economic and environment-friendly.
For achieving the above object, the present invention is by the following technical solutions:
The preparation method of a kind of low odor polypropylene grafted maleic anhydride, comprises the following steps:
(1) polypropylene is added in reactor, evacuation, then with the air in nitrogen replacement reaction kettle, replace 3-10
Secondary, after completing under nitrogen protection, it is warming up to material and all melts；
(2) when temperature rises to 150～230 DEG C, addition styrene and initiator, response time control 10～60min, instead
Evacuation remove impurity after should completing；
(3) when temperature stabilization is at 150～230 DEG C, add maleic anhydride and initiator, react 10～60min, reacted
Evacuation remove impurity 30～120min after one-tenth；
(4), after remove impurity, nitrogen is utilized to be extruded by material, tie rod pelletizing, obtain low odor polypropylene grafted maleic
Acid anhydride.
Preferred as technique scheme, described polypropylene is HOPP or COPP, and its form is
Powdery or granular, melt index (230 DEG C × 2.16kg) is 1～100g/10min, preferably 4～50g/10min.
Preferred as technique scheme, described polypropylene accounts for the 1～100% of gross weight, preferably 80～99%.
Preferred as technique scheme, described maleic anhydride addition is the 0.1～3% of polypropylene weight, preferably
It is 1～3%.
Preferred as technique scheme, described initiator is selected from peroxide type initiators, preferably dual-tert-butyl
Dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, cumyl peroxide, peroxidating uncle
In butyl isopropylbenzene, 3,6,9-triethyl group-3,6,9-trimethyl-1,4,7-three peroxide nonane and di-tert-butyl peroxide one
Plant or multiple mixing.
Preferred as technique scheme, the initiator amount of described step (2) and step (3) is respectively polypropylene weight
The 0.1%～2% of amount, preferably 0.1～1%.
Preferred as technique scheme, described cinnamic consumption is the 0.1～10% of polypropylene weight, is preferably
1～5%.
Preferred as technique scheme, in step (2), described reaction temperature is 160～190 DEG C.
Preferred as technique scheme, in step (3), the temperature of described reaction is 160～190 DEG C.
The method have the advantages that
Maleic anhydride monomer is grafted on the strand of acrylic resin by the present invention by the reaction of melted free radical grafting,
Described melting graft reaction is additionally added auxiliary monomer styrene in addition to adding grafted monomers maleic anhydride, and is drawn by peroxide
Send out agent initiation reaction, be effectively increased the activity of maleic anhydride reaction, thus improve percent grafting；
The present invention utilizes two-step method first to be reacted with polypropylene by styrene, then adds maleic anhydride and carries out grafting instead
Should, utilize two-step method can suitably reduce maleic anhydride and styrene addition on the premise of ensureing higher percent grafting, be prepared into
The graft abnormal smells from the patient arrived is the lightest, and without the addition of other additives such as antioxidant, preparation cost is low, economic and environment-friendly.
Detailed description of the invention:
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
Release the present invention, the present invention will not be constituted any restriction.
Embodiment 1
(1) PP of 1000g is added in reactor, displaces the air in reactor with nitrogen, then heat to 170～
190℃；
(2), after being raised to temperature, under nitrogen protection, 20g styrene and 2g 2,5-dimethyl-2,5-bis-(tert-butyl group mistake are added
Oxidation) hexane, reacts 10～60min；Vacuum remove impurity, removes unreacted styrene and decomposition of initiator product in reaction；
(3) treat that temperature stabilization, at 160～180 DEG C, leads to nitrogen, add 12g maleic anhydride and 2g2,5-dimethyl-2,5-bis-
(tert-butyl hydroperoxide) hexane initiator, reacts 10～60min；Vacuum remove impurity 0.5～1h；
(4) blowing, tie rod, pelletizing, obtain polypropylene grafted maleic anhydride.
Embodiment 2
(1) PP of 1000g is added in reactor, displaces the air in reactor with nitrogen, then heat to 170～
180℃；
(2) constant temperature, under nitrogen protection, adds 15g styrene and 2g 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide)
Hexane, reacts 10～60min；Vacuum remove impurity, removes unreacted styrene and decomposition of initiator product in reaction；
(3) treat that temperature stabilization, at 170～180 DEG C, leads to nitrogen, add 15g maleic anhydride and 2g dual-tert-butyl peroxidating two
Cumene initiator, reacts 10～60min；Vacuum remove impurity 0.5～1h；
(4) blowing, tie rod, pelletizing, prepare polypropylene grafted maleic anhydride.
Embodiment 3
(1) PP of 1000g is added in reactor, displace the air in reactor with nitrogen, be warming up to 170～190
℃；
(2) constant temperature, under nitrogen protection, adds 18g styrene and 2g dual-tert-butyl dicumyl peroxide, reaction 10～
60min；Vacuum remove impurity, removes unreacted styrene and decomposition of initiator product in reaction；
(3) treat that temperature stabilization, at 160～190 DEG C, leads to nitrogen, add 18g maleic anhydride and 2g dual-tert-butyl peroxidating two
Cumene initiator, reacts 10～60min；Vacuum remove impurity 0.5～1h；
(4) blowing, tie rod, pelletizing, prepare polypropylene grafted maleic anhydride.
Comparative example 1
(1) adding in reactor by 1000g PP, evacuation, nitrogen is protected, is warming up to 150～230 DEG C；
(2) constant temperature, under nitrogen protection, adds 12g maleic anhydride, stirs to PP and maleic anhydride mixing (about 30min)；
(3) after temperature constant, adding 20g styrene and 4g 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) is own
Alkane, time for adding controls 1～30min；
About (4) 160～190 DEG C constant temperature, logical nitrogen reaction 30～60min；Reaction terminates rear evacuation and removes unreacted
Impurity.
(5) blowing, tie rod, pelletizing, prepare polypropylene grafted maleic anhydride.
Comparative example 2
(1) adding in reactor by 1000g PP, evacuation, nitrogen is protected, is warming up to 150～230 DEG C；
(2) constant temperature, under nitrogen protection, adds 15g maleic anhydride, stirs to PP and maleic anhydride mixing (about 30min)；
(3) after temperature constant, adding 15g styrene and 4g 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) is own
Alkane, time for adding controls 1～30min；
About (4) 160～190 DEG C constant temperature, logical nitrogen reaction 30～60min；Reaction terminates rear evacuation and removes unreacted
Impurity.
(5) blowing, tie rod, pelletizing, prepare polypropylene grafted maleic anhydride.
Comparative example 3
(1) adding in reactor by 1000g PP, evacuation, nitrogen is protected, is warming up to 150～230 DEG C；
(2) constant temperature, under nitrogen protection, adds 18g maleic anhydride, stirs to PP and maleic anhydride mixing (about 30min)；
(3) after temperature constant, adding 18g styrene and 4g 2,5-dimethyl-2,5-bis-(tert-butyl hydroperoxide) is own
Alkane, time for adding controls 1～30min；
About (4) 160～190 DEG C constant temperature, logical nitrogen reaction 30～60min；Reaction terminates rear evacuation and removes unreacted
Impurity.
(5) blowing, tie rod, pelletizing, prepare polypropylene grafted maleic anhydride.
Below above-mentioned prepared polypropylene grafted maleic anhydride is carried out percent grafting and abnormal smells from the patient test, method of testing and result
As follows:
One, percent grafting test:
(1) refined sample: weigh 2g polypropylene grafted maleic anhydride product and be placed in 500ml boiling flask, add 100ml
Dimethylbenzene, 135 DEG C are heated to reflux to grafting samples all dissolving, and add 80ml acetone while hot, stand cooling 30min, filter, use
Acetone cleans three times, then by 80 DEG C of vacuum drying ovens baking more than 12h of sample placement until constant weight, obtains the polypropylene grafted of purification
Maleic anhydride；
(2) weigh the purified product (quality is designated as m) that about 0.5g step (1) prepares, be dissolved in 100ml dimethylbenzene
In, 135 DEG C are heated to reflux until sample all dissolves, and cool down 5min, drip 0.08mol/L (C1) KOH-ethanol mark with pipet
Quasi-solution 2ml, 135 DEG C are heated to reflux 1h, and cool 30min, add 0.05mol/L (C2) hydrochloric acid aqueous isopropanol 10ml,
135 DEG C are heated to reflux 30min, and cool 30min, drip 2 phenolphthalein, the most again with 0.08mol/L KOH-ethanol solution
The hydrochloric acid of overtitration, the volume that record is consumed is designated as V1；
(3) weighing the blank sample of about 0.5g, repeat step (2), the volume that record is consumed is designated as V2, uses below equation meter
Calculating percent grafting: MAH (%)=9.806* [C1 (V1-V2)]/2m, wherein m is the quality of purification polypropylene grafted maleic anhydride.
Two, graft abnormal smells from the patient test:
(1) weigh 20 ± 2g and treat that test sample is put in odor bottle, and odor bottle is covered tightly put into 80 ± 2 DEG C of constant temperature and force logical
In the baking oven of wind, 80 ± 2 DEG C of constant temperature 2h, when oven temperature is cooled to 60 ± 5 DEG C, open odor bottle lid rapidly and carry out gas
Taste is assessed.
(2) more objective in order to assess, assessment number is at least 3 people (that is assessment panel is at least made up of) 3 people.
Gap between the mark that everyone is given can not be more than 2 points.If scoring gap is more than 2 points, then continue to put into 80 ± 2 DEG C
Baking oven is placed 30min, other 2 people is estimated again.
(3) testing result evaluation grade divides
The evaluation of abnormal smells from the patient can be entered to all possible variable according to opinion rating (as shown in table 1) according to mark 1 to 6
Row scoring, it is also possible to be divided into 0.5 point between mark and carry out.
Table 1
| Grade | Standard |
| 1 | Can not experience |
| 2 | Can experience, unobstructive |
| 3 | Can substantially experience, but there is no the biggest obstruction |
| 4 | There is obstruction |
| 5 | There is bigger obstruction |
| 6 | Insufferable |
Test result is as shown in table 2:
Table 2
From the point of view of above example with the result of comparative example, in the case of maleic anhydride, styrene addition are identical, this
The percent grafting of the polypropylene grafted maleic anhydride that invention prepares is higher, and abnormal smells from the patient is lower, more economical environmental protection.
Claims (9)
1. the preparation method of a low odor polypropylene grafted maleic anhydride, it is characterised in that comprise the following steps:
(1) polypropylene is added in reactor, evacuation, then with the air in nitrogen replacement reaction kettle, replace 3-10 time, complete
After one-tenth under nitrogen protection, it is warming up to material all melt；
(2) when temperature rises to 150～210 DEG C, being initially charged styrene, be stirring evenly and then adding into initiator, the response time controls
10～60min, vacuum remove impurity；
(3) remove impurity is complete, is filled with nitrogen, when maintaining the temperature at 150～210 DEG C, adds maleic anhydride and initiator, reaction 10～
60min, after completion of the reaction evacuation remove impurity 30～120min；
(4), after remove impurity, it is filled with nitrogen and material is extruded, tie rod pelletizing, obtain low odor polypropylene grafted maleic anhydride and produce
Product.
The preparation method of a kind of low odor polypropylene grafted maleic anhydride the most as claimed in claim 1, it is characterised in that: described
Polypropylene be HOPP or COPP, its form is powdery or granular, and melt index (230 DEG C × 2.16kg) is
1～100g/10min, preferably 4～50g/10min.
The preparation method of a kind of low odor polypropylene grafted maleic anhydride the most as claimed in claim 1, it is characterised in that: described
Polypropylene account for the 1～100% of reactant gross weight, preferably 80～99%.
The preparation method of a kind of low odor polypropylene grafted maleic anhydride the most as claimed in claim 1, it is characterised in that: described
Maleic anhydride addition is the 0.1～3% of polypropylene weight, preferably 0.5～1.5%.
The preparation method of a kind of low odor polypropylene grafted maleic anhydride the most as claimed in claim 1, it is characterised in that: described
Initiator be selected from peroxide type initiators, preferably dual-tert-butyl dicumyl peroxide, 2,5-dimethyl-2,5-bis-
(tert-butyl hydroperoxide) hexane, cumyl peroxide, t-butylcumylperoxide, 3,6,9-triethyl group-3,6,9-front three
One or more mixing in base-1,4,7-three peroxide nonane and di-tert-butyl peroxide.
The preparation method of a kind of low odor polypropylene grafted maleic anhydride the most as claimed in claim 1, it is characterised in that: step
(2) initiator amount and described in step (3) is respectively the 0.1～2% of polypropylene weight, preferably 0.1～1%.
The preparation method of a kind of low odor polypropylene grafted maleic anhydride the most as claimed in claim 1, it is characterised in that: described
Cinnamic consumption is the 0.1～10% of polypropylene weight, preferably 1～5%.
The preparation method of a kind of low odor polypropylene grafted maleic anhydride the most as claimed in claim 1, it is characterised in that: step
(2), in, described reaction temperature is preferably 160～190 DEG C.
The preparation method of a kind of low odor polypropylene grafted maleic anhydride the most as claimed in claim 1, it is characterised in that: step
(3), in, the temperature of described reaction is preferably 160～190 DEG C.
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| CN114292363A (en) * | 2021-12-16 | 2022-04-08 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114292363A (en) * | 2021-12-16 | 2022-04-08 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
| CN114292363B (en) * | 2021-12-16 | 2023-11-24 | 佛山(华南)新材料研究院 | High-fluidity maleic anhydride grafted polyethylene and preparation method thereof |
| CN114085324A (en) * | 2021-12-31 | 2022-02-25 | 山东天风新材料有限公司 | Low-odor polypropylene grafted maleic anhydride and preparation method thereof |
| CN114085324B (en) * | 2021-12-31 | 2024-03-26 | 山东天风新材料有限公司 | Low-odor polypropylene grafted maleic anhydride and preparation method thereof |
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| CN106117445B (en) | 2019-01-25 |
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Application publication date: 20161116 Assignee: Zhejiang Hongtian New Material Technology Co.,Ltd. Assignor: ZHEJIANG JAVA SPECIALTY CHEMICALS Co.,Ltd. Contract record no.: X2023980052581 Denomination of invention: A preparation method of low odor polypropylene grafted with maleic anhydride Granted publication date: 20190125 License type: Common License Record date: 20231215 |
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Assignee: Zhejiang Hongtian New Material Technology Co.,Ltd. Assignor: ZHEJIANG JAVA SPECIALTY CHEMICALS Co.,Ltd. Contract record no.: X2023980052581 Date of cancellation: 20240510 |