CN109111534A - A kind of method that temperature-gradient method prepares haloflex - Google Patents
A kind of method that temperature-gradient method prepares haloflex Download PDFInfo
- Publication number
- CN109111534A CN109111534A CN201810672270.5A CN201810672270A CN109111534A CN 109111534 A CN109111534 A CN 109111534A CN 201810672270 A CN201810672270 A CN 201810672270A CN 109111534 A CN109111534 A CN 109111534A
- Authority
- CN
- China
- Prior art keywords
- temperature
- chlorine
- haloflex
- product
- polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 68
- 239000000460 chlorine Substances 0.000 claims abstract description 66
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000004698 Polyethylene Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- -1 polyethylene Polymers 0.000 claims abstract description 21
- 229920000573 polyethylene Polymers 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims abstract description 7
- 239000006004 Quartz sand Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 40
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 230000007717 exclusion Effects 0.000 description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000113 differential scanning calorimetry 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a kind of methods that temperature-gradient method prepares haloflex, by polyethylene, it is added in reaction vessel after initiator mixing, it is passed through nitrogen, 80-85 DEG C is raised the temperature to first, stop logical nitrogen, it is passed through chlorine, after chlorine is full of reaction vessel, adjusting chlorine flowrate is 2%/min~2.5%/min, keep 30-40min, it then proceedes to be warming up to 115 DEG C, chlorination reaction 30-60min, it is further continued for raising the temperature to 130-135 DEG C, keep 40-60min, finally stop logical chlorine, 30-40min is heat-treated at 130-135 DEG C, chlorine atmosphere is kept when heat treatment.The present invention solves the adhesion problem of chlorination reaction product, reduces the residual crystallinity of product, the performance indicator of product meets industrialized standard using gradually heating chlorination and the method for adding quartz sand antitack agent.
Description
Technical field
The present invention relates to a kind of method that solid phase method prepares haloflex, especially a kind of temperature-gradient method preparation chlorination is poly-
The method of ethylene.
Background technique
Haloflex is a kind of novel macromolecular elastomer material, generally can be regarded as ethylene, vinyl chloride, 1,2-
The copolymer of the ternary random arrangement of dichloroethylene.Almost all is the singly-bound of saturation in haloflex molecular chain structure, with-
Based on C-C- is single-stranded, bond energy is high, it is not easy to be broken, be free of active group, have stable chemical structure.Therefore containing there are many excellent
Good characteristic, such as heat resistance, chemical corrosion resistance, anti-flammability, good conductivity and mechanical strength height, can be widely applied to
Plastics, building materials, chemical industry, electric appliance, shipbuilding, coating etc., have a extensive future.
The preparation method of haloflex mainly has solwution method, suspension method and three kinds of solid phase method.Solwution method pollution is big, investment
Height, complex process are eliminated substantially；Though suspension method technical maturity, more advanced, which generates a large amount of acid waste waters, and equipment is rotten
Erosion is serious, and up-front investment is big, and has been unable to meet higher and higher environmental requirement；Solid phase method simple process, investment is small, and product is pure
Only, environmental pollution is small, is a kind of environmental protection, economic technique.
Solid phase method prepares haloflex and remains in the laboratory research stage at present, there are no mature industrialization report
Road.Since the chlorination reaction of polyethylene is strong exothermic reaction, simultaneous reactions temperature is consolidated near the fusing point of polyethylene
Phase method easily causes the bonding foaming and sintering of solid particle to each other when preparing haloflex, cause chlorination uneven, drop
The product residual crystallinity of low chlorination reaction rate, preparation is high, and product quality is lower than product quality prepared by suspension method.Reaction is put
Heat, product bonding and residual crystallinity height are the key points for restricting solid phase method and preparing haloflex technological development, therefore are moved
Except reaction heat, the bonding phenomenon of product is solved, the residual crystallinity for reducing product is the most important thing of the technical study.
Summary of the invention
It is removed to solve reaction heat, product bonding, the problem that chlorination is uneven and residual crystallinity is high.The present invention is main
Provide a kind of method that temperature-gradient method prepares haloflex.This method is easy to operate, invests small, environmental protection and economy, preparation
Product is pure, and residual crystallinity is low and elasticity is good.
A kind of temperature-gradient method prepare the method for haloflex the following steps are included:
100 parts of above-mentioned polyethylene raw materials, 2~4 parts of initiators and 50 parts~60 parts of antitack agent are added after evenly mixing
Enter into temperature programming fixed bed reactors, the air being passed through after connecting in nitrogen exclusion system.
The temperature in reactor is risen to 80~85 DEG C by temperature programming system, heating rate is 2 DEG C/min.Close nitrogen
Air valve, is passed through chlorine, opens chlorine circulation loop valve, after being full of chlorine in reactor, adjust chlorine flowrate be 2%/
Min~2.5%/min, low temperature chlorination react 30~40min.
It then proceedes to be warming up to 115 DEG C with 2 DEG C/min heating rate, 30~60min of chlorination reaction.
It is further continued for being warming up to 130~135 DEG C with 2 DEG C/min heating rate, 40~60min of high-temperature chlorination.
At low temperature, chlorination reaction only carries out on the surface of polyethylene the present invention, and polyethylene surface is formed containing high chlorine dose
Hard shell, the mutual bonding agglomeration between reducing particle when being formed in temperature reaction of hard shell；Antitack agent can be equal
Even dispersion polyethylene particle reduces the contact area of polyethylene particle to each other, while can be absorbed and putting in chlorination reaction
Reaction heat out, to further prevent the bonding of particle.The heating of three steps and antitack agent collective effect, prevent product from bonding,
And remove the heat that reaction generates.
When chlorination reaction temperature is 130~135 DEG C, remaining crystal almost all melting, the strand of inner tight arrangement
It is opened, causes the chlorine radical of generation and the molecule chain reaction of opening, the steric hindrance of generation makes remaining crystallization while cooling
It cannot be restored to original crystalline state, crystal region fundamental transformation is undefined structure.Simultaneously at the heat at 130~135 DEG C
Reason can allow particle surface and the internal macromolecular changing of the relative positions to be homogenized, and chlorination position is avoided excessively to concentrate, to make the chlorine point of product
Cloth tends to the residual crystallinity for uniformly reducing product.It is chlorine atmosphere that system is kept when heat treatment, prevents the chlorinated polyethylene of preparation
The alkene product removing hydrogen chloride gas slight at 130~135 DEG C.
Chlorine valve is finally closed, 30min is heat-treated at 130~135 DEG C, is still chlorine atmosphere in reactor.At heat
After reason, nitrogen valve is opened, closes chlorine circulation valve, the chlorine in exclusion system, chlorine is inhaled through sodium hydroxide solution
It receives.
Haloflex product is taken out after reactor temperature is reduced to room temperature is put into baking with alkali liquid washing to neutrality
It dries in case to constant weight.
One chlorine atom of every increase just has a hydrogen atom and is substituted on the strand of polyethylene, while generating a chlorine
Change hydrogen molecule, the mass change on polyethylene molecular chain is 34.5, and the quality of hydrogen chloride is 36.5.It therefore can be according to saturated common salt
The weight gain of water calculates the chlorinity of haloflex by quantitative relationship.Calculation formula is as follows, and wherein Δ W is chlorine
Change the weight of HCl caused by reacting, W is the weight of polyethylene raw material used in chlorination reaction.
The tail gas that chlorination reaction generates is mainly hydrogen chloride gas and unreacted chlorine, and the hydrogen chloride gas in tail gas can
By removing to saturated salt solution, remaining unabsorbed pure chlorine is repeatable by circulation loop after drying in tail gas
It utilizes.
Initiator used in chlorination reaction is azodiisobutyronitrile or benzoyl peroxide；Antitack agent used is not cross 40
The quartz sand of mesh screen.
The beneficial effects of the present invention are:
Using gradually temperature-raising method, mutual bonding agglomeration between particle is avoided, prevents product from bonding, and remove reaction and generate
Heat, make product chlorine be distributed tend to uniformly, reduce the residual crystallinity of product.
Use the main indicator of haloflex product prepared by the present invention: chlorinity is 38%~41%, remnants knot
Brilliant degree < 2%, heat-stable time >=502s, residue of combustion < 3%, volatile content < 0.3%, hardness are 55~70, are drawn
Stretching intensity is 8~12MPa, and elongation at break is 650%~750%.
The present invention solves chlorination reaction product using gradually heating chlorination and the method for adding quartz sand antitack agent
Adhesion problem, reduces the residual crystallinity of product, and the elasticity of chlorine atom being evenly distributed on strand, product increases, produces
The index for the product that the performance indicator of product is prepared with suspension method is not much different, and meets industrialized standard.
Detailed description of the invention
Fig. 1 is the differential scanning calorimetry figure of haloflex product.
Fig. 2 is the infrared spectrum spectrogram of haloflex product.
Fig. 3 is the nuclear magnetic resonance spectroscopy spectrogram of haloflex product.
Specific embodiment
Below by specific embodiment, the present invention is further explained:
The key industry index request of the product of suspension method preparation are as follows: chlorinity 30%-40%, melting heat≤2J/g, Shao
Family name hardness≤70, tensile strength >=8MPa, elongation at break >=500%, volatile content≤0.3%, heat-stable time >=
8min, residue of combustion≤4.5%.
Comparative example 1
A, the preparation of aaerosol solution: the hydrochloric acid solution of 4000L 10% being added into the acid-resistant reacting kettle of 5000L, stirs shape
Melt index (MI) MI (190 DEG C/5kg)=0.2-l.0g/l0min is added under state, MFR is the high density polyethylene (HDPE) 400kg of 10-30,
And 1.0kg dispersing agent fatty alcohol polyoxyethylene ether, 2.0kg antitack agent white carbon black, obtained aaerosol solution is stirred evenly, then will
Acid-resistant reacting kettle sealing.
Chlorination reaction: b is divided to two sections to be passed through chlorine into the aaerosol solution and carries out chlorination reaction:
Warming-up section: originating logical chlorine temperature control is 75 DEG C, is gradually heated to 130 DEG C, it is 220kg that warming-up section, which leads to chlorine dose,；
Constant temperature zone: the control of constant temperature zone temperature is 130 DEG C, and temperature is kept constant, and leading to chlorine dose is 220kg；
Entire reaction process controls logical 75-130 DEG C of chlorine temperature, and being passed through amount of chlorine is 440kg, reaction time 4h.
Separating, washing: reaction terminates, and chlorizate cooling down to temperature of reaction kettle is lower than 80 DEG C, with compress wind by object
Material, which is transported in vacuum filter, carries out vacuum filter, and the HCl recovery filtered out utilizes, filtered chlorizate water
After washing repeatedly, after centrifuge dehydration and heated-air drying, then grind through grinding, feed bin is homogenized to obtain product haloflex,
Chlorinity is 34.0%, DSC2.5J/g, shore hardness 67.
Comparative example 2
The preparation of aaerosol solution: a the hydrochloric acid solution of 8700L 17%, stirring is added into the acid-resistant reacting kettle of 12500L
Melt index (MI) MI (190 DEG C/5kg)=0.2-l.0g/l0min is added under state, the high density that MFR is 10-30 is poly-
Ethylene 1300kg and 1.6kg polyethylene of dispersing agent adjoins pyrrolidone, and 2kg antitack agent D17 stirs evenly obtained aaerosol solution, so
Acid-resistant reacting kettle is sealed afterwards.
Chlorination reaction: b is divided to two sections to be passed through chlorine into the aaerosol solution and carries out chlorination reaction:
Warming-up section: originating logical chlorine temperature control is 60 DEG C, is gradually heated to 130 DEG C, it is 780kg that warming-up section, which leads to chlorine dose,；
Constant temperature zone: the control of constant temperature zone temperature is 130 DEG C, and temperature is kept constant, and leading to chlorine dose is 520kg；
Entire reaction process controls logical 60-130 DEG C of chlorine temperature, and being passed through amount of chlorine is 1300kg, reaction time 4.5h.
C, separating, washing: reaction terminates, and chlorizate cooling down to temperature of reaction kettle is lower than 80 DEG C, will with compress wind
Material, which is transported in vacuum filter, carries out vacuum filter, and the HCl recovery filtered out utilizes, and filtered chlorizate is used
After water washs repeatedly, after centrifuge dehydration and heated-air drying, then grind through grinding, feed bin is homogenized to obtain product haloflex,
Its chlorinity is 33.3%, DSC2.0J/g, shore hardness 69.
Comparative example 3
The preparation of suspension Lip river liquid: a the hydrochloric acid Lip river liquid of 8000L 25%, stirring is added into the acid-resistant reacting kettle of 12500L
Melt index (MI) MI (190 DEG C/5kg)=0.2-1.0g/10min is added under state, MFR is the high density polyethylene (HDPE) of 10-30
1600kg and 3kg dispersing agent methyl acrylate monomethyl acrylic copolymer, 8kg antitack agent talcum powder, stir evenly obtained
Then aaerosol solution seals acid-resistant reacting kettle.
Chlorination reaction: b is divided to two sections to be uniformly passed through chlorine into the aaerosol solution and carries out chlorination reaction:
Warming-up section: originating logical chlorine temperature control is 30 DEG C, is gradually heated to 125 DEG C, it is 800kg that warming-up section, which leads to chlorine dose,；
Constant temperature zone: constant temperature zone temperature essence is made as 125 DEG C, and temperature is kept constant, and leading to chlorine dose is 350kg:
Entire reaction process controls logical 30-125 DEG C of chlorine temperature, is passed through amount of chlorine 1150kg, reaction time 5h.
C, separating, washing: reaction terminates, and chlorizate cooling down to temperature of reaction kettle is lower than 80 DEG C, will with compress wind
Material, which is transported in vacuum filter, carries out vacuum filter, and the HCl recovery filtered out utilizes, and filtered chlorizate is used
After water washs repeatedly, after centrifuge dehydration and heated-air drying, then grind through grinding, feed bin is homogenized to obtain product haloflex,
Its chlorinity is 22%, DSC3.0J/g, shore hardness 70.
Embodiment 1
It is 68.7% by 100 parts of crystallinity, fusing point is 134.3 DEG C, and partial size is 150~380um, and wax content 1.2% melts
Body flow rate is 0.804g/10min, specific surface area 3.344 × 10-3cm3.g-1 of 2.047m2.g-1, Kong Rongwei, branching
Degree adds after evenly mixing for 5.65 polyethylene raw material, 3 parts of benzoyl peroxide initiators and 60 parts of quartz sand antitack agent
Enter into temperature programming fixed bed reactors, the air being passed through after connecting in nitrogen exclusion system.Pass through temperature programming system
Temperature in reactor is risen to 85 DEG C, heating rate is 2 DEG C/min.Nitrogen valve is closed, chlorine is passed through, opens chlorine circulation
Circuit valve, after being full of chlorine in reactor, adjusting chlorine flowrate is 2.5%/min, and low temperature chlorination reacts 40min.Then
Continue to be warming up to 115 DEG C with 2 DEG C/min heating rate, chlorination reaction 60min.It is further continued for being warming up to 2 DEG C/min heating rate
130 DEG C, high-temperature chlorination 30min.Chlorine valve is finally closed, 30min is heat-treated at 130 DEG C, is still chlorine in reactor
Atmosphere is enclosed.After heat treatment, nitrogen valve is opened, closes chlorine circulation valve, the chlorine in exclusion system, chlorine is through hydrogen-oxygen
Change sodium solution to absorb.Haloflex product is taken out after reactor temperature is reduced to room temperature to be put with alkali liquid washing to neutrality
Enter in baking oven and dries to constant weight.
Use the main indicator of haloflex product prepared by the present invention: chlorinity 36%, residual crystallinity <
2%, heat-stable time 498s, residue of combustion 0.98%, volatile content 0.199%, hardness 60, tensile strength
For 10.1MPa, elongation at break 690%.
Embodiment 2
It is 68.7% by 100 parts of crystallinity, fusing point is 134.3 DEG C, and partial size is 150~380um, and wax content 1.2% melts
Body flow rate is 0.804g/10min, specific surface area 3.344 × 10-3cm3.g-1 of 2.047m2.g-1, Kong Rongwei, branching
Degree adds after evenly mixing for 5.65 polyethylene raw material, 2 parts of azodiisobutyronitrile initiators and 50 parts of quartz sand antitack agent
Enter into temperature programming fixed bed reactors, the air being passed through after connecting in nitrogen exclusion system.Pass through temperature programming system
Temperature in reactor is risen to 80 DEG C, heating rate is 2 DEG C/min.Nitrogen valve is closed, chlorine is passed through, opens chlorine circulation
Circuit valve, after being full of chlorine in reactor, adjusting chlorine flowrate is 2%/min, and low temperature chlorination reacts 30min.Then after
It is continuous to be warming up to 115 DEG C with 2 DEG C/min heating rate, high-temperature chlorination 30min.It is further continued for the heating of 2 DEG C/min heating rate
To 130 DEG C, high-temperature chlorination 60min.Chlorine valve is finally closed, 30min is heat-treated at 130 DEG C, is still in reactor
Chlorine atmosphere.After heat treatment, nitrogen valve is opened, closes chlorine circulation valve, the chlorine in exclusion system, chlorine is through hydrogen
Sodium hydroxide solution absorbs.Haloflex product is taken out after reactor temperature is reduced to room temperature, with alkali liquid washing to neutrality,
It is placed in oven and dried to constant weight.
Use the main indicator of haloflex product prepared by the present invention: chlorinity 41%, residual crystallinity <
2%, heat-stable time 505s, residue of combustion 1%, volatile content 0.209%, hardness 57, tensile strength are
10.5MPa, elongation at break 750%.
For the product index comparison such as following table of industrial products index request, comparative example and embodiment, by that can be seen in table
The haloflex product of Solid phase synthesis of the invention can satisfy the requirement of current industrialization product out, and compare the prior art
Suspension method preparation properties of product it is more excellent.
Claims (7)
1. a kind of method that temperature-gradient method prepares haloflex, it is characterised in that: be added after mixing polyethylene, initiator anti-
It answers in container, is passed through nitrogen, raise the temperature to 80-85 DEG C first, stop logical nitrogen, be passed through chlorine, chlorine holds full of reaction
After device, adjusting chlorine flowrate is 2%/min~2.5%/min, keeps 30-40min, then proceedes to be warming up to 115 DEG C, chlorination is anti-
30-60min is answered, is further continued for raising the temperature to 130-135 DEG C, keeps 40-60min, finally stops logical chlorine, in 130-135
It is heat-treated 30-40min at DEG C, when heat treatment keeps chlorine atmosphere.
2. a kind of method that temperature-gradient method prepares haloflex as described in claim 1, it is characterised in that: heating rate is
2℃/min。
3. a kind of method that temperature-gradient method prepares haloflex as described in claim 1, it is characterised in that: polyethylene is height
Density polyethylene, crystallinity 68.7%, fusing point are 134.3 DEG C, and partial size is 150~380um, wax content 1.2%, specific surface
Product is 2.047m2.g-1, Kong Rongwei 3.344 × 10-3cm3.g-1, melt flow rate (MFR) 0.804g/10min, the degree of branching is
5.65。
4. a kind of method that temperature-gradient method prepares haloflex as described in claim 1, it is characterised in that: initiator is even
Nitrogen bis-isobutyronitrile or benzoyl peroxide, dosage are the 2%~4% of polyethylene quality.
5. a kind of method that temperature-gradient method prepares haloflex as described in claim 1, it is characterised in that: with polyethylene,
The also antitack agent that initiator mixes simultaneously, antitack agent are the quartz sand for not crossing 40 mesh screens, after reaction can be with product
It is kept completely separate, dosage is the 50%~60% of polyethylene quality.
6. a kind of method that temperature-gradient method prepares haloflex as described in claim 1, it is characterised in that: heat treatment finishes
Afterwards, stop heating, be passed through nitrogen, exclude the chlorine in reaction vessel, chlorine absorbs what removing generated through saturated sodium chloride solution
Hydrogen chloride gas, it is reusable by circulation loop after remaining unabsorbed dry chlorine in tail gas.
7. a kind of method that temperature-gradient method prepares haloflex as described in claim 1, it is characterised in that: in reaction vessel
Temperature is down to room temperature, removes haloflex product, dry with alkali liquid washing to neutrality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810672270.5A CN109111534A (en) | 2018-06-26 | 2018-06-26 | A kind of method that temperature-gradient method prepares haloflex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810672270.5A CN109111534A (en) | 2018-06-26 | 2018-06-26 | A kind of method that temperature-gradient method prepares haloflex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109111534A true CN109111534A (en) | 2019-01-01 |
Family
ID=64822540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810672270.5A Pending CN109111534A (en) | 2018-06-26 | 2018-06-26 | A kind of method that temperature-gradient method prepares haloflex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109111534A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372472A (en) * | 2021-07-09 | 2021-09-10 | 瑞易德新材料股份有限公司 | Production process of ester-soluble chlorinated polyethylene |
| CN115140960A (en) * | 2022-06-21 | 2022-10-04 | 上海城建物资有限公司 | Anti-caking agent, premix, soil body curing agent, and preparation and application thereof |
| CN115368049A (en) * | 2022-07-21 | 2022-11-22 | 上海城建物资有限公司 | Efficient anti-caking agent and preparation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4425206A (en) * | 1982-12-09 | 1984-01-10 | The Dow Chemical Company | Anhydrous process for preparing amorphous chlorinated polyethylene and product thereof |
| CN85106428A (en) * | 1985-08-28 | 1987-03-18 | 湖北省化学研究所 | The solid-phase chlorination method of snappiness chlorinatedpolyethylene |
| CN86100452A (en) * | 1986-01-14 | 1987-08-05 | 青岛化工学院 | The preparation method of chlorinatedpolyolefins |
| CN86106365A (en) * | 1986-09-12 | 1988-03-23 | 青岛化工学院 | The preparation method of polyolefine chloride coatings |
| CN1125734A (en) * | 1994-12-28 | 1996-07-03 | 青岛昌泰祥工贸有限公司 | Preparation method of high chlorinated polyethylene |
-
2018
- 2018-06-26 CN CN201810672270.5A patent/CN109111534A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4425206A (en) * | 1982-12-09 | 1984-01-10 | The Dow Chemical Company | Anhydrous process for preparing amorphous chlorinated polyethylene and product thereof |
| CN85106428A (en) * | 1985-08-28 | 1987-03-18 | 湖北省化学研究所 | The solid-phase chlorination method of snappiness chlorinatedpolyethylene |
| CN86100452A (en) * | 1986-01-14 | 1987-08-05 | 青岛化工学院 | The preparation method of chlorinatedpolyolefins |
| CN86106365A (en) * | 1986-09-12 | 1988-03-23 | 青岛化工学院 | The preparation method of polyolefine chloride coatings |
| CN1125734A (en) * | 1994-12-28 | 1996-07-03 | 青岛昌泰祥工贸有限公司 | Preparation method of high chlorinated polyethylene |
Non-Patent Citations (6)
| Title |
|---|
| 王展望: "氯化聚乙烯专用HDPE树脂L0555P ", 《石油科技论坛》 * |
| 王展望: "氯化聚乙烯专用HDPE树脂L0555P", 《石油科技论坛》 * |
| 赵季若，冯莺，顾娟英，曹桂芳，杨玉伟: "固相法氯化聚乙烯改性聚氯乙烯的研究 ", 《青岛化工学院学报》 * |
| 赵季若，冯莺，顾娟英，曹桂芳，杨玉伟: "固相法氯化聚乙烯改性聚氯乙烯的研究", 《青岛化工学院学报》 * |
| 赵季若等: "氯化聚乙烯弹性体的固相法合成 ", 《应用化学》 * |
| 赵季若等: "氯化聚乙烯弹性体的固相法合成", 《应用化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372472A (en) * | 2021-07-09 | 2021-09-10 | 瑞易德新材料股份有限公司 | Production process of ester-soluble chlorinated polyethylene |
| CN115140960A (en) * | 2022-06-21 | 2022-10-04 | 上海城建物资有限公司 | Anti-caking agent, premix, soil body curing agent, and preparation and application thereof |
| CN115140960B (en) * | 2022-06-21 | 2024-04-09 | 上海城建物资有限公司 | Anti-caking agent, premix, soil body curing agent, and preparation and application thereof |
| CN115368049A (en) * | 2022-07-21 | 2022-11-22 | 上海城建物资有限公司 | Efficient anti-caking agent and preparation and application thereof |
| CN115368049B (en) * | 2022-07-21 | 2024-04-26 | 上海城建物资有限公司 | Efficient anti-caking agent and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109111534A (en) | A kind of method that temperature-gradient method prepares haloflex | |
| WO2011069281A1 (en) | Perfluorinated ion exchange resin, preparation method and use thereof | |
| CN102260361B (en) | Preparation method of chlorinated polyethylene | |
| CN113024732B (en) | Near-infrared light response N-isopropyl acrylamide-based hydrogel and preparation method and application thereof | |
| CN106188405A (en) | Graft modification super high molecular weight micronized polyethylene and solid phase grafting method thereof | |
| CN112608412B (en) | Preparation method of fluorine-containing grafted polyolefin material | |
| Guan et al. | A facile one-pot route to transparent polymer nanocomposites with high ZnS nanophase contents via in situ bulk polymerization | |
| US4760113A (en) | Process for continuously producing a high-melt viscoelastic ethylene-propylene copolymer | |
| CN113214418A (en) | Preparation method of high-porosity polyvinyl chloride | |
| CN104291384A (en) | Method for producing polymeric ferric sulfate | |
| CN107266614A (en) | A kind of super high molecular weight haloflex and preparation method thereof, device and application | |
| CN108912544A (en) | A kind of high temperature resistant PVC box material and preparation method thereof | |
| CN103182255A (en) | Manufacturing method for polystyrene/polyvinylidene anion exchange alloy membrane | |
| CN109134717A (en) | A kind of solid phase method of temperature-gradient method prepares the production technology of haloflex | |
| CN110183324A (en) | A kind of preparation process of stearate | |
| CN103818886B (en) | A kind of preparation method of cadmium telluride | |
| CN108948547A (en) | A kind of method that suspension chlorination reaction prepares oil-filled type chlorinated polyethylene rubber | |
| CN108503930A (en) | A kind of preparation method of modified poly ethylene geomembrane | |
| WO2022111289A1 (en) | Ablation-resistant silicon-boron-nitrogen rubber and preparation method therefor | |
| CN1301272C (en) | Reversible addition-fragmentation chain transfer free radical polymerization method | |
| CN108752802A (en) | A kind of preparation method of heatproof modification plastic particle | |
| CN102351971B (en) | Preparation method of chlorination butyl rubber | |
| CN102079800A (en) | Preparation method of semiconductive high-water-absorptivity resin | |
| CN105754040A (en) | High-liquidity heat-resistant PVC (polyvinyl chloride) resin and preparation method thereof | |
| CN110510643A (en) | A kind of method that cryogenic vacuum system efficiently utilizes magnesium chloride slag to obtain high-purity magnesium oxide high molecular fire retardant material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190101 |
|
| RJ01 | Rejection of invention patent application after publication |