CN104592656A - Polymer compatibilizer with universality and preparation method thereof - Google Patents
Polymer compatibilizer with universality and preparation method thereof Download PDFInfo
- Publication number
- CN104592656A CN104592656A CN201510038690.4A CN201510038690A CN104592656A CN 104592656 A CN104592656 A CN 104592656A CN 201510038690 A CN201510038690 A CN 201510038690A CN 104592656 A CN104592656 A CN 104592656A
- Authority
- CN
- China
- Prior art keywords
- universality
- hydroxyethyl
- polymer
- solid
- methyl methacrylate
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004793 Polystyrene Substances 0.000 claims abstract description 28
- 229920002223 polystyrene Polymers 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 23
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004698 Polyethylene Substances 0.000 claims abstract description 19
- -1 polyethylene Polymers 0.000 claims abstract description 19
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000573 polyethylene Polymers 0.000 claims abstract description 17
- 239000001384 succinic acid Substances 0.000 claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 84
- 239000007787 solid Substances 0.000 claims description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 42
- 238000005516 engineering process Methods 0.000 claims description 38
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 24
- 238000012986 modification Methods 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005453 pelletization Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- 238000011010 flushing procedure Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229920006942 ABS/PC Polymers 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention relates to a polymer compatibilizer with universality. The polymer compatibilizer with universality comprises the following components in parts by weight: 20-35 parts of octa-epoxy modified silsesquioxane, 5-10 parts of mono-hydroxyl-terminated polystyrene, 5-10 parts of methyl methacrylate-(2-hydroxyethyl) methacrylate copolymer, 5-10 parts of hydroxyl-terminated polyethylene, 1-5 parts of N,N-diisopropylethylamine and 0.1-0.5 part of succinic acid. The invention also relates to a preparation method of the compatibilizer. The polymer compatibilizer has the advantages that the polarity and rigidity of the three polymer molecular skeletons including polystyrene, the methyl methacrylate-(2-hydroxyethyl) methacrylate copolymer and polyethylene can represent the properties of most polymers for general use; the polymer compatibilizer obtained by combining polystyrene, the methyl methacrylate-(2-hydroxyethyl) methacrylate copolymer and polyethylene can well satisfy the aim of recovery of most polymer alloys and waste plastics, thus greatly expanding the range of application of the compatibilizer; the polymer compatibilizer with a multi-arm and miktoarm star structure is constructed by using octa-epoxy modified silsesquioxane, thus increasing the grafting ratio of the compatibilizer.
Description
Technical field
The present invention relates to compatilizer technical field, concrete finger is a kind of can be applicable to the universality Its Compatibilizing Technology of the aspect such as recycling of inorganic modified, waste or used plastics of high polymer alloy, polymkeric substance, the invention still further relates to the preparation method of above-mentioned universality Its Compatibilizing Technology.
Background technology
At present, the application of plastics in all trades and professions is that other material is incomparable, and along with the progress of social productive forces and the development of science and technology, the homopolymer of single variety can not meet the day by day harsh demand of industry-by-industry already.Under constantly attempting and making great efforts, people have developed various segmented copolymer, as ABS plastic, SBS plastics etc., and high polymer alloy numerous in variety, as PP/PE, PP/PA, PA/PS, PA/ABS, ABS/PC, PBT/PA, PET/PA, PP/POE, PE/EPDM, TPE/PU etc.
In order to give more novel, various performance to polymer materials further, in recent years, the inorganic modified research of research staff to polymkeric substance of every profession and trade is very paid attention to.Because the physics between different polymkeric substance and between polymkeric substance and mineral filler, chemical property differ greatly, the two combination is easily separated, thus is difficult to obtain desired product.In order to address this problem, interfacial compatibilizer arises at the historic moment.
Compatilizer is also known as expanding material, it thermodynamically can be understood as interfacial agent, the consistency of two kinds of polymkeric substance can be increased, bonding force between two kinds of polymkeric substance is increased, reduce interfacial tension, increase interfacial layer thickness thus make two-phase compatible, making disperse phase and external phase evenly, form stable structure.Why compatilizer can make the polymer-compatible of two kinds of different in kinds, is to carry out physics or chemically combined group with two kinds of polymkeric substance respectively because have in the molecule thereof.Interfacial compatibilizer is generally that the functional groups such as carboxyl or anhydride group is contained in one end, so that with the active group generation graft reaction of other matrix, and non-polar group is contained in the other end one end of interfacial compatibilizer, for being combined by double-bond polymerization or physical entanglement with nonpolar matrix.
At present, the most widely used on market is Its Compatibilizing Technology with maleic anhydride graft, and it introduces strong polar reaction group by grafted maleic anhydride, thus improves the consistency between polymkeric substance or between mineral filler and polymer materials.But the toxicity ratio of maleic anhydride is comparatively large, and considering from environment protection, is not a kind of safe and reliable selection; Meanwhile, maleic anhydride is only directly received on long polyolefinic main chain with the form of a monomer usually, and the very low interfacial compatibilizer melt fluidity causing preparing of percentage of grafting is poor.Also have the application of the compatilizer of some other types comparatively extensive, such as epoxy type, imide-type, the compatilizer such as isocyanate-based, but the Its Compatibilizing Technology of they and maleic anhydride graft has a common shortcoming, namely the scope of application is narrow.
Therefore, for compatilizer of the prior art, research and develop a kind of universality compatilizer applied widely and seem particularly necessary.
Summary of the invention
Technical problem to be solved by this invention is the present situation for prior art, provides a kind of percentage of grafting high, applied widely and environment amenable universality Its Compatibilizing Technology.
Another technical problem to be solved by this invention is the present situation for prior art, provides a kind of preparation method of above-mentioned universality Its Compatibilizing Technology.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of universality Its Compatibilizing Technology, it is characterized in that comprising following component by weight:
The structural formula of above-mentioned octa-epoxy modification silsesquioxane is as follows:
As preferably, the relative molecular weight of described methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer is 8000 ~ 13000, and molecular weight distribution index is 1.04.
Preferably, in described methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer, the chain unit ratio of methacrylic ester and methyl methacrylate is 1: 15 ~ 20.
Further preferably, the relative molecular weight of described one-ended hydroxy polystyrene is 50000 ~ 100000, and molecular weight distributing index is 1.2; The poly relative molecular weight of described terminal hydroxy group is 20000 ~ 70000, and molecular weight distributing index is 1.18.
A preparation method for above-mentioned universality Its Compatibilizing Technology, is characterized in that comprising the following steps:
(1) in tank reactor, 20 ~ 35g octa-epoxy modification silsesquioxane is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L, and 0.5 ~ 2.5gN is added in this tank reactor, N-diisopropylethylamine, then low whipping speed is 10 ~ 20r/min, still reaction actuator temperature is under the condition of 30 ~ 50 DEG C, five batches that 5 ~ 10g one-ended hydroxy polystyrene are divided into equivalent add successively in tank reactor, continue stirring reaction 4 ~ 5h after adding;
(2) the mixed solution evaporate to dryness in step (1) after completion of the reaction tank reactor is obtained solid A, then be the washed with ether gained solid A of tetrahydrofuran (THF) usage quantity 3 ~ 5 times in step (1) with volume, and by the dry 2 ~ 3h at 50 ~ 60 DEG C of the solid A after flushing;
(3) the solid A after step (2) being processed is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L again, then 0.5 ~ 2.5g N is added, N-diisopropylethylamine, and low whipping speed be 10 ~ 20r/min, temperature is under the condition of 30 ~ 50 DEG C, five batches that 5 ~ 10g methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer are divided into equivalent add, continue stirring reaction 4 ~ 5h after adding;
(4) step (3) mixture evaporate to dryness is after completion of the reaction obtained solid B, then this solid B and 5 ~ 10g terminal hydroxy group polyethylene are carried out mixing 24 ~ 28h at 80 ~ 100 DEG C, finally add 0.1 ~ 0.5g succinic acid and continue discharging after mixing 1 ~ 2h, extruding pelletization, namely obtain described universality Its Compatibilizing Technology.
As improvement, in step (1), the joining day of every batch of one-ended hydroxy polystyrene is not less than 10min, and the interval time that adjacent two batches of one-ended hydroxy polystyrene add is 15min; In step (3), the joining day of every batch of methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer is not less than 10min, and the interval time that adjacent two batches of methyl methacrylates-(2 hydroxyethyl) alkylmethacrylate polymer adds is 20min.The compatilizer each arm number adopting the above-mentioned mode in batches added can make finally to obtain is more even.
Compared with prior art, the invention has the advantages that:
(1) in the present invention, the polarity of polystyrene, methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer and these three kinds of polymer molecule skeletons of polyethylene and rigidity can represent the character of most of polymers for general use, this three combines the object that the Its Compatibilizing Technology obtained can well meet most of high polymer alloy, technics of reclaim of plastic waste, greatly extends the scope of application of compatilizer;
(2) polystyrene of one-ended hydroxy modification is employed herein, the polyethylene of terminal hydroxy group modification, make it possess and be convenient to the active group with other grafting compounds, octa-epoxy modification silsesquioxane then serves the effect connecting base in Its Compatibilizing Technology, octa-epoxy modification silsesquioxane passes through its cage structure by one-ended hydroxy polystyrene, terminal hydroxy group polyethylene and methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer are fixed in a core, construct a kind of multi-arm to mix the Its Compatibilizing Technology of arm star structure, such molecular structure is compared to linear polymer compatilizer of the prior art, more easily reduce interfacial tension, stable interface character, and one-ended hydroxy polystyrene, the end of terminal hydroxy group polyethylene and methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer all remains active group, be convenient to the consistency being improved polymkeric substance and mineral filler by hydrogen bond or epoxy addition reaction, realize high filling, thus improve the stretching of product, the mechanical properties such as resistance to impact shock,
(3) N is adopted in the present invention, N-diisopropylethylamine is as basic catalyst, the epoxy addition reaction of catalysis octa-epoxy modification silsesquioxane one-ended hydroxy polystyrene, terminal hydroxy group polyethylene and methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer, thus make compatilizer of the present invention have higher percentage of grafting; And if other basic catalyst sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood etc. conventional in use prior art replace N, N-diisopropylethylamine, the then silsesquioxane core of destructible Its Compatibilizing Technology, cause the percentage of grafting of one-ended hydroxy polystyrene, terminal hydroxy group polyethylene and methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer lower, and then affect the practical application effect of compatilizer;
(4) compatilizer production process of the present invention easily controls, and whole process is safety low-poison, and the raw materials such as solvent can reuse, environmentally friendly, improves the market competitiveness of compatilizer.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
Wherein, the structural formula of octa-epoxy modification silsesquioxane is as follows:
The preparation method of above-mentioned universality Its Compatibilizing Technology comprises the following steps:
(1) in tank reactor, octa-epoxy modification silsesquioxane is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L, and 2g N is added in this tank reactor, N-diisopropylethylamine, then low whipping speed is 10r/min, still reaction actuator temperature is under the condition of 30 DEG C, five batches that one-ended hydroxy polystyrene are divided into equivalent add in tank reactor successively, the interval time that adjacent two batches of one-ended hydroxy polystyrene add is 15min, continues stirring reaction 5h after adding;
(2) the mixed solution evaporate to dryness in step (1) after completion of the reaction tank reactor is obtained solid A, then be the washed with ether gained solid A of tetrahydrofuran (THF) usage quantity 3 times in step (1) with volume, and by the solid A dry 2.5h at 55 DEG C after flushing;
(3) the solid A after step (2) being processed is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L again, then 2g N is added, N-diisopropylethylamine, and low whipping speed be 12r/min, temperature is under the condition of 30 DEG C, five batches that methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer are divided into equivalent add successively, the interval time that adjacent two batches of methyl methacrylates-(2 hydroxyethyl) alkylmethacrylate polymer adds is 20min, continues stirring reaction 4h after adding;
(4) step (3) mixture evaporate to dryness is after completion of the reaction obtained solid B, then this solid B and terminal hydroxy group polyethylene are carried out mixing 28h at 80 DEG C, finally add succinic acid and continue discharging after mixing 1.5h, extruding pelletization, namely obtain universality Its Compatibilizing Technology.
Embodiment 2:
In the present embodiment, universality Its Compatibilizing Technology comprises following component by weight:
Wherein, the structural formula of octa-epoxy modification silsesquioxane is as follows:
The preparation method of above-mentioned universality Its Compatibilizing Technology comprises the following steps:
(1) in tank reactor, octa-epoxy modification silsesquioxane is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L, and 1.5g N is added in this tank reactor, N-diisopropylethylamine, then low whipping speed is 10r/min, still reaction actuator temperature is under the condition of 40 DEG C, five batches that one-ended hydroxy polystyrene are divided into equivalent add in tank reactor successively, the interval time that adjacent two batches of one-ended hydroxy polystyrene add is 15min, continues stirring reaction 4.5h after adding;
(2) the mixed solution evaporate to dryness in step (1) after completion of the reaction tank reactor is obtained solid A, then be the washed with ether gained solid A of tetrahydrofuran (THF) usage quantity 4 times in step (1) with volume, and by the solid A dry 2h at 60 DEG C after flushing;
(3) the solid A after step (2) being processed is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L again, then 1.5g N is added, N-diisopropylethylamine, and low whipping speed be 18r/min, temperature is under the condition of 45 DEG C, five batches that methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer are divided into equivalent add successively, the interval time that adjacent two batches of methyl methacrylates-(2 hydroxyethyl) alkylmethacrylate polymer adds is 20min, continues stirring reaction 4.5h after adding;
(4) step (3) mixture evaporate to dryness is after completion of the reaction obtained solid B, then this solid B and terminal hydroxy group polyethylene are carried out mixing 25h at 90 DEG C, finally add succinic acid and continue discharging after mixing 2h, extruding pelletization, namely obtain universality Its Compatibilizing Technology.
Embodiment 3:
In the present embodiment, universality Its Compatibilizing Technology comprises following component by weight:
Wherein, the structural formula of octa-epoxy modification silsesquioxane is as follows:
The preparation method of above-mentioned universality Its Compatibilizing Technology comprises the following steps:
(1) in tank reactor, octa-epoxy modification silsesquioxane is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L, and 2.5g N is added in this tank reactor, N-diisopropylethylamine, then low whipping speed is 20r/min, still reaction actuator temperature is under the condition of 50 DEG C, five batches that one-ended hydroxy polystyrene are divided into equivalent add in tank reactor successively, the interval time that adjacent two batches of one-ended hydroxy polystyrene add is 15min, continues stirring reaction 4h after adding;
(2) the mixed solution evaporate to dryness in step (1) after completion of the reaction tank reactor is obtained solid A, then be the washed with ether gained solid A of tetrahydrofuran (THF) usage quantity 5 times in step (1) with volume, and by the solid A dry 3h at 50 DEG C after flushing;
(3) the solid A after step (2) being processed is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L again, then 2.5g N is added, N-diisopropylethylamine, and low whipping speed be 20r/min, temperature is under the condition of 50 DEG C, five batches that methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer are divided into equivalent add successively, the interval time that adjacent two batches of methyl methacrylates-(2 hydroxyethyl) alkylmethacrylate polymer adds is 20min, continues stirring reaction 5h after adding;
(4) step (3) mixture evaporate to dryness is after completion of the reaction obtained solid B, then this solid B and terminal hydroxy group polyethylene are carried out mixing 27h at 100 DEG C, finally add succinic acid and continue discharging after mixing 1h, extruding pelletization, namely obtain universality Its Compatibilizing Technology.
Embodiment 4:
In the present embodiment, universality Its Compatibilizing Technology comprises following component by weight:
Wherein, the structural formula of octa-epoxy modification silsesquioxane is as follows:
The preparation method of above-mentioned universality Its Compatibilizing Technology comprises the following steps:
(1) in tank reactor, octa-epoxy modification silsesquioxane is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L, and 0.5g N is added in this tank reactor, N-diisopropylethylamine, then low whipping speed is 18r/min, still reaction actuator temperature is under the condition of 35 DEG C, five batches that one-ended hydroxy polystyrene are divided into equivalent add in tank reactor successively, the interval time that adjacent two batches of one-ended hydroxy polystyrene add is 15min, continues stirring reaction 4.2h after adding;
(2) the mixed solution evaporate to dryness in step (1) after completion of the reaction tank reactor is obtained solid A, then be the washed with ether gained solid A of tetrahydrofuran (THF) usage quantity 4 times in step (1) with volume, and by the solid A dry 2.7h at 58 DEG C after flushing;
(3) the solid A after step (2) being processed is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L again, then 0.5g N is added, N-diisopropylethylamine, and low whipping speed be 10r/min, temperature is under the condition of 35 DEG C, five batches that methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer are divided into equivalent add successively, the interval time that adjacent two batches of methyl methacrylates-(2 hydroxyethyl) alkylmethacrylate polymer adds is 20min, continues stirring reaction 4.8h after adding;
(4) step (3) mixture evaporate to dryness is after completion of the reaction obtained solid B, then this solid B and terminal hydroxy group polyethylene are carried out mixing 26h at 85 DEG C, finally add succinic acid and continue discharging after mixing 1.8h, extruding pelletization, namely obtain universality Its Compatibilizing Technology.
Embodiment 5:
In the present embodiment, universality Its Compatibilizing Technology comprises following component by weight:
Wherein, the structural formula of octa-epoxy modification silsesquioxane is as follows:
The preparation method of above-mentioned universality Its Compatibilizing Technology comprises the following steps:
(1) in tank reactor, octa-epoxy modification silsesquioxane is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L, and 1.5g N is added in this tank reactor, N-diisopropylethylamine, then low whipping speed is 12r/min, still reaction actuator temperature is under the condition of 45 DEG C, five batches that one-ended hydroxy polystyrene are divided into equivalent add in tank reactor successively, the interval time that adjacent two batches of one-ended hydroxy polystyrene add is 15min, continues stirring reaction 4.8h after adding;
(2) the mixed solution evaporate to dryness in step (1) after completion of the reaction tank reactor is obtained solid A, then be the washed with ether gained solid A of tetrahydrofuran (THF) usage quantity 3 times in step (1) with volume, and by the solid A dry 2.8h at 57 DEG C after flushing;
(3) the solid A after step (2) being processed is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L again, then 2.5g N is added, N-diisopropylethylamine, and low whipping speed be 15r/min, temperature is under the condition of 45 DEG C, five batches that methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer are divided into equivalent add successively, the interval time that adjacent two batches of methyl methacrylates-(2 hydroxyethyl) alkylmethacrylate polymer adds is 20min, continues stirring reaction 4.2h after adding;
(4) step (3) mixture evaporate to dryness is after completion of the reaction obtained solid B, then this solid B and terminal hydroxy group polyethylene are carried out mixing 24h at 95 DEG C, finally add succinic acid and continue discharging after mixing 1.6h, extruding pelletization, namely obtain universality Its Compatibilizing Technology.
Compatilizer prepared by above-described embodiment 1 is applied in nylon 6/ ABS block polymer alloy (PA6/ABS), and the different material property adding ratio of test.Concrete, by PA6 (1013B), ABS (P/D181 high glue powder) respectively at 110 DEG C and 80 DEG C of dry 4h, then according to PA6: ABS: compatilizer: butyl stearate: the weight ratio of oxidation inhibitor 1035 is respectively 70: 30: 0: 0.5: 0.1,70: 30: 3: 0.5: 0.1,70: 30: 5: 0.5: 0.1 and carries out mixing at 180 DEG C, then uses twin screw extruder extruding pelletization; Twin screw extruder temperature is set as 220 DEG C, engine speed 200r/min; Pellet adopts injection moulding machine to be injection molded into standard test specimen after 100 DEG C of dry 4h, and carries out performance test to this sample, and concrete test result is as shown in table 1.
Compatilizer prepared by above-described embodiment 1 is applied to and reclaims polyethylene terephthalate (PET) with styrene-butadiene-styrene block copolymer (SBS) blending and modifying.Concrete, according to PET: SBS: compatilizer: butyl stearate: the weight ratio of antioxidant 264 is respectively 70: 30: 0: 0.5: 0.1,70: 30: 3: 0.5: 0.1,70: 30: 5: 0.5: 0.1 and carries out mixing at 200 DEG C, then uses twin screw extruder extruding pelletization; Twin screw extruder temperature is set as 260 DEG C, engine speed 250r/min; Pellet adopts injection moulding machine to be injection molded into standard test specimen after 100 DEG C of dry 4h, and carries out performance test to this sample, and concrete test result is as shown in table 1.
Compatilizer prepared by above-described embodiment 1 is applied in polypropylene (PP) and wood flour composite material.Concrete, PP: wood powder: compatilizer: lubricant stearic acid butyl ester: antioxidant 1076: the weight ratio of softening agent Polycizer W 260 is respectively 70: 30: 0: 0.5: 0.1: 0.1,70: 30: 3: 0.5: 0.1: 0.1,70: 30: 5: 0.5: 0.1: 0.1 and carries out mixing, bottom sheet at 170 DEG C, then at 175 DEG C, on vulcanizing press, be pressed into the sheet material of standard thickness, then on omnipotent sanction model machine, obtained sheet material is cut into sample by each standard, carry out performance test, concrete test result is as shown in table 1.
The performance test results of not adding compatilizer prepared by the present invention in above-mentioned each material is also listed in table 1.Wherein, the testing method of tensile strength, flexural strength, notched Izod impact strength is respectively according to GB/T 1040.2-2006 " the mensuration part 2 of plastic tensile performance: the test conditions of molding and extrusion molding plastics ", GB/T 9341-2000 " Plastics-Oetermination of flexural properties method " and GB/T 1843-2008 " mensuration of plastics cantilever beam impact strength ".
Table 1
As can be seen from Table 1, use the com-patibilising effect between the compatilizer latter two differing materials prepared by the present invention better, material has better mechanical property.
Octa-epoxy modification silsesquioxane in the present invention buys the EP0435 from Hybrid Plastics company of the U.S., the P9071-SOH from Canadian Polymer Source company bought by one-ended hydroxy polystyrene, the P2890-EOH from Canadian Polymer Source company bought by terminal hydroxy group polyethylene, methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer buys the P13152A-MMAHEMA from Canadian Polymer Source company, N, N-diisopropylethylamine buys from 496219 of Sigma Aldrich company of the U.S., succinic acid buys the S3674 from SigmaAldrich company of the U.S..
Claims (7)
1. a universality Its Compatibilizing Technology, is characterized in that comprising following component by weight:
2. universality Its Compatibilizing Technology according to claim 1, is characterized in that: the structural formula of described octa-epoxy modification silsesquioxane is as follows:
3. universality Its Compatibilizing Technology according to claim 1, is characterized in that: the relative molecular weight of described methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer is 8000 ~ 13000, and molecular weight distribution index is 1.04.
4. universality Its Compatibilizing Technology according to claim 3, is characterized in that: in described methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer, the chain unit ratio of methacrylic ester and methyl methacrylate is 1: 15 ~ 20.
5. universality Its Compatibilizing Technology according to claim 1, is characterized in that: the relative molecular weight of described one-ended hydroxy polystyrene is 50000 ~ 100000, and molecular weight distributing index is 1.2; The poly relative molecular weight of described terminal hydroxy group is 20000 ~ 70000, and molecular weight distributing index is 1.18.
6. a preparation method for the universality Its Compatibilizing Technology in Claims 1 to 5 described in arbitrary claim, is characterized in that comprising the following steps:
(1) in tank reactor, 20 ~ 35g octa-epoxy modification silsesquioxane is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L, and 0.5 ~ 2.5gN is added in this tank reactor, N-diisopropylethylamine, then low whipping speed is 10 ~ 20r/min, still reaction actuator temperature is under the condition of 30 ~ 50 DEG C, five batches that 5 ~ 10g one-ended hydroxy polystyrene are divided into equivalent add successively in tank reactor, continue stirring reaction 4 ~ 5h after adding;
(2) the mixed solution evaporate to dryness in step (1) after completion of the reaction tank reactor is obtained solid A, then be the washed with ether gained solid A of tetrahydrofuran (THF) usage quantity 3 ~ 5 times in step (1) with volume, and by the dry 2 ~ 3h at 50 ~ 60 DEG C of the solid A after flushing;
(3) the solid A after step (2) being processed is dissolved in tetrahydrofuran (THF) in the ratio of 1kg/10L again, then 0.5 ~ 2.5g N is added, N-diisopropylethylamine, and low whipping speed be 10 ~ 20r/min, temperature is under the condition of 30 ~ 50 DEG C, five batches that 5 ~ 10g methyl methacrylate-(2 hydroxyethyl) alkylmethacrylate polymer are divided into equivalent add successively, continue stirring reaction 4 ~ 5h after adding;
(4) step (3) mixture evaporate to dryness is after completion of the reaction obtained solid B, then this solid B and 5 ~ 10g terminal hydroxy group polyethylene are carried out mixing 24 ~ 28h at 80 ~ 100 DEG C, finally add 0.1 ~ 0.5g succinic acid and continue discharging after mixing 1 ~ 2h, extruding pelletization, namely obtain described universality Its Compatibilizing Technology.
7. preparation method according to claim 6, is characterized in that: the interval time that in step (1), adjacent two batches of one-ended hydroxy polystyrene add is 15min; The interval time that adjacent two batches of methyl methacrylates in step (3)-(2 hydroxyethyl) alkylmethacrylate polymer adds is 20min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510038690.4A CN104592656B (en) | 2015-01-27 | 2015-01-27 | A kind of universality Its Compatibilizing Technology and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510038690.4A CN104592656B (en) | 2015-01-27 | 2015-01-27 | A kind of universality Its Compatibilizing Technology and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104592656A true CN104592656A (en) | 2015-05-06 |
| CN104592656B CN104592656B (en) | 2017-01-04 |
Family
ID=53118739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510038690.4A Expired - Fee Related CN104592656B (en) | 2015-01-27 | 2015-01-27 | A kind of universality Its Compatibilizing Technology and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104592656B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033456A (en) * | 2017-04-28 | 2017-08-11 | 东华大学 | One kind is based on POSS organic-inorganic hybrid nanometers compatilizer and its preparation and application |
| CN109989128A (en) * | 2019-03-11 | 2019-07-09 | 东华大学 | The nylon fiber and preparation method thereof that skin-friction coefficient is low and hydrophobicity improves |
| CN111961276A (en) * | 2020-08-18 | 2020-11-20 | 大连工业大学 | Polyethylene composite material containing long-chain alkyl modified silsesquioxane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702735A (en) * | 2012-01-19 | 2012-10-03 | 五行材料科技（江苏）有限公司 | Highly-filled enhanced PA 66 composite material and preparation method thereof |
| CN103205104A (en) * | 2013-05-06 | 2013-07-17 | 湖南工业大学 | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane) hybridized polylactic acid/polycarbonate alloy |
-
2015
- 2015-01-27 CN CN201510038690.4A patent/CN104592656B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702735A (en) * | 2012-01-19 | 2012-10-03 | 五行材料科技（江苏）有限公司 | Highly-filled enhanced PA 66 composite material and preparation method thereof |
| CN103205104A (en) * | 2013-05-06 | 2013-07-17 | 湖南工业大学 | Preparation method of POSS (Polyhedral Oligomeric Silsesquioxane) hybridized polylactic acid/polycarbonate alloy |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107033456A (en) * | 2017-04-28 | 2017-08-11 | 东华大学 | One kind is based on POSS organic-inorganic hybrid nanometers compatilizer and its preparation and application |
| CN109989128A (en) * | 2019-03-11 | 2019-07-09 | 东华大学 | The nylon fiber and preparation method thereof that skin-friction coefficient is low and hydrophobicity improves |
| CN109989128B (en) * | 2019-03-11 | 2020-06-02 | 东华大学 | Nylon fiber with low surface friction coefficient and improved hydrophobicity and preparation method thereof |
| CN111961276A (en) * | 2020-08-18 | 2020-11-20 | 大连工业大学 | Polyethylene composite material containing long-chain alkyl modified silsesquioxane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104592656B (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101735604B (en) | A kind of montmorillonite modified PA6/ABS alloy material and preparation method thereof | |
| CN101709125B (en) | Polystyrene/polyolefin nano composite material based on interface compatibilization and preparation method thereof | |
| CN103360674A (en) | Wood powder composite foam material and preparation method thereof | |
| CN109666219B (en) | Polypropylene/shear thickening gel composite material and application thereof in bumper | |
| CN102643484A (en) | In-situ compatibilization polyolefin/polystyrene alloy and preparation method and application thereof | |
| CN103540074B (en) | Compatilizer master batch for high filled polyolefin material and preparation method thereof | |
| CN102174270A (en) | Plasticized and toughened wood flour/polypropylene composite and method for preparing same | |
| CN102516464B (en) | Epoxypropyl methacrylate grafting acrylonitrile butadiene styrene (ABS) copolymer and preparation method thereof | |
| CN119613858A (en) | High-performance composite board prepared by utilizing waste wind power blades and preparation method thereof | |
| CN104592656A (en) | Polymer compatibilizer with universality and preparation method thereof | |
| CN101967296A (en) | A kind of bamboo-plastic composite foam material and preparation method thereof | |
| CN115678020B (en) | Degradable lignin polypropylene composite material and preparation method thereof | |
| CN103113741B (en) | Novel modified PA66 (polyamide 66) material and preparation method thereof | |
| CN103102639B (en) | A kind of acrylonitrile butadient styrene composite and preparation method | |
| CN102585431B (en) | Preparation method of ABS (Acrylonitrile Butadiene Styrene)-based wood-plastic composite | |
| KR20170011520A (en) | Impact strength modifiers, method for preparing the same, and polylactic acid/polycarbonate resin composition | |
| CN112661911B (en) | Multi-monomer grafted polylactic acid compatilizer and preparation method and application thereof | |
| CN104844767A (en) | Toughening compatilizer containing polyphenyl ether and polyamide | |
| JP6619150B2 (en) | Method for producing expanded molded article of carbon fiber reinforced / modified polyethylene terephthalate resin | |
| CN105924999A (en) | Toughening type modified wood-plastic composite material and preparation method thereof | |
| CN109721928B (en) | Polypropylene composition and preparation method and application thereof | |
| CN107955270B (en) | Polypropylene nano composite material and preparation method thereof | |
| JP2017186492A (en) | Method for producing expanded molded article of carbon fiber reinforced / modified polypropylene resin | |
| CN115703854B (en) | A compatibilizer and its application in the preparation of polyolefin/polysaccharide polymer composite materials | |
| CN109206713A (en) | A kind of preparation method and application of the Recycled HDPE composite material containing Poplar Powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170104 Termination date: 20220127 |