CN107090064B - A method of macromonomer, preparation method with more alkyl structures and polymer polyatomic alcohol is prepared using it - Google Patents
A method of macromonomer, preparation method with more alkyl structures and polymer polyatomic alcohol is prepared using it Download PDFInfo
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- CN107090064B CN107090064B CN201710373473.XA CN201710373473A CN107090064B CN 107090064 B CN107090064 B CN 107090064B CN 201710373473 A CN201710373473 A CN 201710373473A CN 107090064 B CN107090064 B CN 107090064B
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- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
Abstract
The invention discloses a kind of macromonomer with more alkyl structures, preparation method and the methods for preparing polymer polyatomic alcohol with it, using basic polyether polyalcohol as continuous phase, polymer polyatomic alcohol is prepared under the action ofs chain-transferring agent, radical initiator etc. in macromonomer with more alkyl structures；Decomposition of initiator product can be used as the raw material that preparation has the macromonomer of more alkyl structures, realizes recycling for chemical substance, improves atom utilization, reduces generation and the three-protection design of poisonous and harmful waste residue.
Description
Technical field
Polymer is prepared the present invention relates to a kind of macromonomer with more alkyl structures and preparation method thereof, using it
The method of polyalcohol.Specifically, being related to a kind of big point of toxic waste preparation using in polymer polyatomic alcohol preparation process
Sub- monomer, in the presence of the macromonomer is as stabilizer, it is more to prepare polymer for in-situ polymerization in basic polyether polyalcohol
The method of first alcohol.
Background technique
Polymer polyatomic alcohol is large industrial products, can assign polyurethane product good load-carrying properties, and improve
The opening of foam.Polymer polyatomic alcohol is that one or more of vinyl monomers are poly- in situ by continuous phase of basic polyether polyalcohol
It closes.The vinyl monomer that the polymer polyatomic alcohol synthesized earliest uses is acrylonitrile, and product solid content is low, and viscosity is big,
Under 30% contains admittedly, the viscosity with 10000cp (25 DEG C) is not able to satisfy the use of modernization large-scale precision equipment, while product
Color number is relatively deep, and core is easily burnt in foamed product jaundice.
To solve the above problems, people have carried out a large amount of research work, there are many new technologies.United States Patent (USP)
It proposes to solve polymer polyatomic alcohol yellowish and foam with two or more vinyl monomer copolymerization in US4208314
The problem of burning core, preferred styrene and acrylonitrile monemer are copolymerized, and are closed when styrene monomer is greater than acrylonitrile monemer in monomer ratio
At polymer polyatomic alcohol product be white, the burning core problem of foamed product is improved.The shortcomings that such method be with
The increase of styrene-content, product viscosity increase, and conversion ratio reduces, and the dispersion stabilization of system is deteriorated.
It is disclosed in Chinese publication CN201410494201.1 and CN201410558934.7 semicontinuous and continuous
The method that technique prepares polymer polyatomic alcohol.By increasing the side dissolved with solvent or the performed polymer for preparing noresidue monomer
The problem of production processes such as method improves easy fouling present in conventional preparation techniques, viscosity is big, particle size is big.
Although the above method solves the problems, such as product polymer polyalcohol solid big containing low and viscosity, but does not mention initiator azo
The processing problem of the decomposition product tetramethyl succinonitrile (TMSN) of bis-isobutyronitrile (AIBN), tetramethyl succinonitrile easily distil, severe toxicity,
Biochemical treatment low efficiency, difficulty are big；Burning is also easy to produce oxynitrides, and incomplete combustion can generate the HCN of severe toxicity.
These drawbacks existing in the prior art are solved, needing to find a kind of can be used in preparing polymer polyatomic alcohol
Novel monomeric.
Summary of the invention
The object of the present invention is to provide a kind of macromonomers with more alkyl structures.It is particularly a kind of to use more alkane
Base fourth diisocyanate, with double bond structure hydroxyl value compound and macromolecular polyether polyol react preparation more alkyl knots
The macromonomer of structure.
It is a further object of the present invention to provide the preparation methods of the macromonomer.It is prepared by raw material of tetramethyl succinonitrile
Macromonomer, by being carried out plus hydrogen to raw material, phosgenation, purification again with hydroxyl value compound and macromolecular with double bond structure
The macromonomer of more alkyl structures of polyether polyol reaction preparation.
Another object of the present invention is to provide the method for preparing polymer polyatomic alcohol using the macromonomer.Use more alkane
Based structures macromonomer, in the presence of polyether polyol with the mixing of styrene, acrylonitrile or other ethylenically unsaturated monomers
After object polymerization, the de- good polymer polyatomic alcohol of high solids content, low viscosity, dispersion stabilization singly obtained, which meets green
The requirement of color Atom economy.
To realize the above goal of the invention, the invention adopts the following technical scheme:
A kind of macromonomer with more alkyl structures, structure are as follows:
Wherein, R1、R2、R3、R4、R5And R6Separately indicate polyethylene oxide segment and/or polypropylene oxide segments；
R1、R2、R3、R4、R5And R6In 6 segments the weight ratio of polypropylene oxide segments summation and polyethylene oxide segment summation be 3~
19；
R7、R8、R9And R10Separately indicate methyl, ethyl, isobutyl group；It is preferred that R7With R9Identical expression methyl, R8With
R10Identical expression methyl, ethyl, isobutyl group；More preferable R7、R8、R9And R10Identical expression methyl；
R11Indicate H or methyl；
R12For-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)CH2Or-CH2(CH3)CH-。
In the present invention, the average weight-average molecular weight of the segment is 1100~2800, and the average weight-average molecular weight of segment is
Refer to R1、R2、R3、R4、R5And R6Again divided by 6 after the weight average molecular weight adduction of 6 segments；
In the present invention, as a preferred solution, macromonomer (the abbreviation macromolecular with more alkyl structures
Monomer), structure is as follows:
The heretofore described macromonomer preparation method with more alkyl structures, comprising the following steps:
Diisocyanate with containing double bond structure hydroxy compounds and macromolecular polyether polyol under conditions of catalyst
Reaction prepares macromonomer；
It describes according to the present invention, the preparation of the macromonomer can be prepared by one-step technology, can also be passed through
The preparation of performed polymer multistep processes technique；
It describes according to the present invention, the performed polymer multistep processes technique is diisocyanate and the hydroxy compound containing double bond structure
Object reaction in the presence of catalyst c-1 prepares performed polymer, and performed polymer is again with macromolecular polyether polyol in the presence of catalyst c-2
Reaction preparation has the macromonomer of more alkyl structures.
The diisocyanate ester structure are as follows:Wherein R7, R8、R9And R10Separately
Indicate methyl, ethyl, isobutyl group；It is preferred that R7With R9Identical expression methyl, R8With R10Identical expression methyl, ethyl, isobutyl group；More
It is preferred that R7、R8、R9And R10Identical expression methyl；
The diisocyanate is preferably tetramethyl fourth diisocyanate (TMBDI), two isocyanide of dimethyl diisobutyl fourth
One of acid esters and dimethyl diethyl fourth diisocyanate are a variety of；More preferably tetramethyl fourth diisocyanate
In the present invention, the hydroxy compounds containing double bond structure includes but is not limited to hydroxyethyl methacrylate
(HEMA), one of hydroxy propyl methacrylate, hydroxy-ethyl acrylate and hydroxypropyl acrylate or a variety of, preferably metering system
Sour hydroxyl ethyl ester (HEMA).The molar ratio of the diisocyanate and the hydroxy compounds containing double bond structure is 1/3~3/1, preferably
1/1。
In the present invention, the molar ratio of the diisocyanate and macromolecular polyether polyol is 1/3~3/1, preferably 1/1.
In the present invention, the catalyst, catalyst c-1 and catalyst c-2, separately selected from tertiary amine catalyst and/
Or organo-metallic compound；The tertiary amine catalyst be selected from N, N- dimethyl cyclohexyl amine, bis- (2- dimethylaminoethyl) ethers, N, N,
N', N'- tetramethyl Alkylenediamine, triethylamine, N, N- dimethyl benzylamine, N-ethylmorpholine,N-methylmorpholine, N, N'- diethyl
Base piperazine, triethanolamine, N, N- diformazan ethyl glycol (DMEA)And one of N, N'- lutidines etc. or a variety of；It is described
Organo-metallic catalyst is selected from one of metallic tin, potassium, lead, mercury, bismuth and zinc etc. or a variety of carboxylate and/or metal alkyl
Compound.
Performed polymer multistep processes technique is prepared in macromonomer technique, and by weight, the catalyst c-1 dosage is containing double
The 0.001%~5% of the hydroxy compounds of bond structure, preferably 0.01%~2%.The catalyst c-2 dosage is poly- for macromolecular
The 0.001%~3% of ethoxylated polyhydric alcohol, preferably 0.005%~2%.
It as a kind of implementable solution, can choose after preparing macromonomer, using a small amount of acid in system
Catalyst carries out fire extinguishing processing, such as phosphoric acid.
In the present invention, the macromolecular polyether polyol is to do initiator with sorbierite, through propylene oxide and ethylene oxide
Open loop is prepared, and the macromolecular polyether polyol hydroxyl value control is in 20~48mgKOH/g, preferably 24~33mgKOH/g.
The macromolecular polyether polyol structural formula is as follows:
Wherein R1、R2、R3、R4、R5And R6Separately indicate polyethylene oxide segment and/or polypropylene oxide segments；
The average weight-average molecular weight of segment is 1100~2800, and the average weight-average molecular weight of segment indicates R1、R2、 R3、R4、
R5And R6Again divided by 6 after the weight average molecular weight adduction of 6 segments；
R1、R2、R3、R4、R5And R6The weight of polypropylene oxide segments summation and polyethylene oxide segment summation in 6 segments
Amount is than being 3~19；.
In the present invention, the reaction temperature that the diisocyanate prepares performed polymer with the hydroxy compounds containing double bond structure is
0~80 DEG C, preferably 40~60 DEG C；Reaction time preferably 0.1~5 hour, more preferable 1~2 hour.
The reaction temperature of heretofore described performed polymer and macromolecular polyether polyol be 40~100 DEG C, preferably 60~80
℃；Reaction time preferably 0.1~5 hour, more preferable 1~3 hour.
It is described according to the present invention, in the preparation process of macromonomer, polymerization inhibitor can be optionally added, as one kind
Implementable solution, the polymerization inhibitor include but is not limited to hydroquinone, p-tert-Butylcatechol, p-hydroxyanisole, methyl
One of quinhydrones, phenthazine and diphenylamines are a variety of.By weight, the dosage of the polymerization inhibitor is macromolecular polyether polyol
The 0~1.5% of product population, preferably 30~2000ppm.
As an example, selecting tetramethyl fourth diisocyanate (TMBDI) is diisocyanate, hydroxyethyl methacrylate second
Ester (HEMA) is double bond containing hydroxy compounds, the reaction process of the macromonomer prepared by the present invention with more alkyl structures
It is as follows:
It describes according to the present invention, the source of the diisocyanate includes but is not limited to that commercially available buying obtains and passes through
Dintrile is prepared.
In the present invention, the method for preparing polymer polyatomic alcohol using the macromonomer with more alkyl structures, packet
Include following steps:
1) intermittently operated is used, the macromonomer with more alkyl structures mixes conduct with part basis polyether polyol
Reaction kettle is added in bottom material；
2) after heating bottom material, by remaining basic polyether polyalcohol, chain-transferring agent, initiator, ethylenically unsaturated monomer chemical combination
Object mixing is continuously added to reaction kettle as liftout, and certain pressure and temperature is kept in reaction process, is removed not after being added dropwise
Monomer, chain-transferring agent and the decomposition of initiator product of reaction, obtain polymer polyatomic alcohol.
The method that the present invention prepares polymer polyatomic alcohol further include:
3) the decomposition of initiator product for the crystallization that distils in vacuum system is collected.
In the present invention, the selection of the basic polyether polyalcohol is determined by the final use of polymer polyatomic alcohol, example
If polymer polyatomic alcohol is used for the production of the soft bubble of massive polyurethane, general soft polyurethane foam polyether polyol is just selected, generally
Hydroxyl value is the basic polyether polyalcohol of the three-functionality-degree of 54~58mgKOH/g；For the production of high rebound foam, high return just is selected
Foam polyether polyol is played, general hydroxyl value is the basic polyether of the three-functionality-degree of the high activity on the right side 33.5~36.5mgKOH/g
Polyalcohol.The heretofore described preferred hydroxyl value of basic polyether polyalcohol is the polyether polyols of the three-functionality-degree of 54~58mgKOH/g
Alcohol is as basic polyether polyol.
It include that all be generally accepted is suitable for preparing polymer polyol suitable for ethylenically unsaturated monomer of the invention
The vinyl monomer of alcohol, including but not limited to aliphatic conjugated diene, vinyl aromatic compounds, α, β-olefinically unsaturated nitriles,
α, β-olefinically unsaturated nitriles amide, α, β-ethylenically unsaturated carboxylic acids, α, β-ethylenically unsaturated carboxylic acids ester, vinyl esters, vinyl
One of ether, vinyl ketone, vinyl and vinylidene halide are a variety of；Preferred vinyl aromatic compound and olefinic are not
Saturated nitriles；Particularly preferred styrene and acrylonitrile, more preferable weight ratio are 10: 90~90: 10, preferably 60: 40~90: 10 benzene
Ethylene and acrylonitrile；The mass ratio of the ethylenically unsaturated monomer and basic polyether polyalcohol is 0.1%~200%, preferably
30%~140%.
In the present invention, by weight, dosage is that basic polyether polyols are pure and mild to the macromonomer with more alkyl structures
The 0.3%~10% of ethylenically unsaturated monomer compound gross mass, preferably 2%~5%.
In the present invention, the quality of basic polyether polyalcohol in the step 1) and step 2) of the method for polymer polyatomic alcohol is prepared
Than being 1/10~10/1, preferably 1/2~2/1.
The temperature that bottom material heats in step 2) is 80~140 DEG C, preferably 90~120 DEG C；The reaction temperature of step 2) is 80
~150 DEG C, preferably 90~120 DEG C, pressure (gauge pressure) are 0~0.6Mpa, preferably 0.05~0.4MPa.
Described according to the present invention, the chain-transferring agent selected in polymer polyatomic alcohol preparation process can be isopropanol, benzene, first
Benzene, mercaptan, halogenated hydrocarbons, water or their mixture, preferably isopropanol；By weight, based on the chain-transferring agent dosage
The 1%~10% of the pure and mild ethylenically unsaturated monomer compound gross mass of polyether polyols, preferably 3%~5%.
In the preparation of Inventive polymers polyalcohol, the initiator is selected from azodiisobutyronitrile, azobisisoheptonitrile, idol
One of nitrogen diisoamyl nitrile is a variety of, preferably azodiisobutyronitrile.By weight, the initiator amount is that basic polyethers is more
The pure and mild ethylenically unsaturated monomer compound gross mass of member O.3%~O.5%.
Description according to the present invention, the heat exchanger of the vacuum system of step 3) cleaning preferably easy to disassemble.
According to the present invention it is described be collected into decomposition of initiator product tetramethyl succinonitrile, dimethyl diisobutyl succinonitrile,
Dimethyl diethyl succinonitrile etc. can continue through the purification process such as dry or recrystallization, also can be directly used for preparing in the present invention
Macromonomer raw material uses.
The tetramethyl succinonitrile, dimethyl diisobutyl succinonitrile, removing for dimethyl diethyl succinonitrile are used as by-product
Outside, source includes but is not limited to that commercially available buying is obtained and is prepared by corresponding azo dintrile.
It describes, is prepared using the decomposition of initiator product of the present invention big with more alkyl structures according to the present invention
The method of the raw material diisocyanate of molecule monomer, comprising the following steps:
A) after decomposition of initiator product is dissolved with solvent, in the presence of catalyst a, hydrogenation reaction is carried out, is refining to obtain and contains
There is the hydrogenation reaction solution of diamines；
B) phosgenation reaction is carried out to the diamines of step a) and obtains diisocyanate.
Four are then prepared for example, the decomposition of initiator product is tetramethyl succinonitrile as a kind of implementable solution
The process of methyl fourth diisocyanate is as follows:
Solvent used in step a) includes but is not limited to the solvent that alcohol, hydrocarbon, amide, amine and ether etc. can be used for hydrogenation reaction
One of or a variety of, one of preferred alcohol, isopropanol, toluene, benzene, tetrahydrofuran and dioxane or a variety of, it is more excellent
Select isopropanol；The mass content of decomposition of initiator product is 0.5~20%, preferably 10~16% in solution.
It describes according to the present invention, the hydrogenation conditions are that reaction pressure is 5~10MPa (absolute pressure), hydrogenation reaction
Temperature is 50~100 DEG C；Describe according to the present invention, step a) use autoclave, under the conditions of having ammonia or without ammonia with hydrogen
Reaction.Liquefied ammonia can be used as inhibitor and be optionally added into, and the molar ratio of ammonia and decomposition of initiator product is 0~30:1.
Describe according to the present invention, the optional self-contained Raney's nickel of the catalyst a, thunder Buddhist nun cobalt, Lei Nitong and support type it is expensive
One of metallic catalyst is a variety of, preferably thunder Buddhist nun cobalt.
Describe according to the present invention, step a) hydrogenation reaction solution after deamination, desolventizing, rectifying diamines, then again into
The phosgenation reaction of row step b).
Step b) diamines phosgenation reaction of the present invention can be gas phase phosgenation, can also be liquid phase phosgenation, preferably exists
It is carried out in dicyandiamide solution, available solvent is halogenated aryl hydrocarbon, aromatic hydrocarbons, carbon tetrachloride, chloroform, organic amide etc., preferably chloro
Benzene, toluene, more preferable chlorobenzene or dichloro-benzenes；Photochemical reaction temperature is 60~100 DEG C, preferably 70~90 DEG C；Aging temperature is
130~180 DEG C, preferably 140~160 DEG C.
The beneficial effects of the present invention are:
Novel macromonomer prepared by the present invention is used to prepare POP product, can obtain under lower usage amount
Good product index.
Initiator used in Inventive polymers polyols preparation process, decomposition product can be used as big point of the invention
The raw material of sub- monomer realizes atom and reuses and do not generate poisonous and harmful substance, realizes green chemical industry production.
The preparation method of polymer polyatomic alcohol according to the present invention, compared with the prior art, whole process realize closed circuit follow
Ring does not generate poisonous and hazardous solid waste, solves the problems, such as traditional handicraft solid waste, reduces the cost of the processing three wastes.
Specific embodiment
By specific embodiment example, the present invention will be described in detail.The scope of the present invention is not with specific embodiment
It is limited, but is defined in the claims.
Hydroxyl value: GB 12008.3-2009 plastics polyether polyol third portion: the measurement of hydroxyl value；
Viscosity: the 7th part of GB 12008.7-2010 plastics polyether polyol: the measurement of viscosity；
Degree of unsaturation: the 6th part of GB 12008.6-2010 plastics polyether polyol: the measurement of degree of unsaturation；
Admittedly containing: GB/T 31062-2014 polymer polyatomic alcohol；
Embodiment 1
1) tetramethyl succinonitrile adds hydrogen to prepare tetramethyl butane diamine:
The aqueous isopropanol for being dissolved with 40g tetramethyl succinonitrile (collection of vacuum heat exchanger) is added in tank reactor
160g, ammonia 50g, 25%KOH aqueous solution 0.16g, thunder Buddhist nun Co catalysts 10g, Hydrogen Vapor Pressure 8MPa, reaction temperature is 80 DEG C,
400 revs/min of progress hydrogenation reactions of speed of agitator.It is warming up to 95 DEG C again, keeps pressure 10Mpa, the reaction was continued 1h takes out after cooling
Reaction solution after removing liquefied ammonia and solvent, collects 90~100 DEG C of liquid at 100mbar, and weigh 30.4g.
2) tetramethyl butane diamine prepares tetramethyl fourth diisocyanate TMBDI:
400ml chlorobenzene is placed in 1 liter of reaction kettle, is stirred, the air that nitrogen excludes dissolution is blasted, then passes to drying
HCl gas and a small amount of nitrogen, flow velocity 80L/h separately take chlorobenzene solution (the 30g tetramethyl butane diamine of 30ml tetramethyl butane diamine
It is uniformly mixed with 150ml chlorobenzene) it is added in 60min by peristaltic pump sample introduction into aforesaid reaction vessel, then it is passed through dry HCl about
30min.Nitrogen purging is replaced, solution slowly heats up, and is warming up to 80 DEG C, keeps the temperature 30min, reduces logical nitrogen flow.Nitrogen purging
After, it is passed through phosgene, flow velocity 10g/min, and be slowly warming up to 150 DEG C, keeps this temperature until solution is clarified, stopping is logical
Phosgene simultaneously stops heating.It is passed through the remaining phosgene of nitrogen purging, terminates experiment after 30min, photochemical liquid removes molten through vacuum distillation
The photochemical liquid of agent, concentration obtains product TMBDI by rectifying.
3) preparation of macromolecular polyether polyol 1
The use of sorbierite is initiator, catalyst (KOH) concentration is the 0.3% of PO mass, control reaction temperature 110 ±
Between 5 DEG C, pressure is reacted lower than 0.15MPa, the aging 2h to the end of PO feeds intake, and deaerate 1h.Start to throw EO after degassing,
Reaction temperature is controlled between 110 ± 5 DEG C, pressure is reacted lower than 0.15MPa, aging 2h after feeding intake, and deaerate 1h,
The stage of reaction terminates at this time.Temperature is controlled at 85-90 DEG C, soft water is added and phosphoric acid neutralizes, is dehydrated, filtering, cooling discharge.Wherein
Sorbierite/EO/PO mass ratio is 1.08/4.95/93.97, and the polyalcohol hydroxyl value is about 28mgKOH/g after measured.
4) preparation of macromonomer 1:
By the tetramethyl fourth diisocyanate (TMBDI, 34.94g) of above-mentioned preparation, stannous octoate catalyst (air chemical industry,
300mg) and hydroquinone (Rhodia, 130mg) is added in well-mixed reaction vessel and is heated to 50 DEG C.Then it adds
Hydroxyethyl methacrylate (HEMA, commercially available, 23.17g) simultaneously stirs reaction mixture 1.5 hours, prepares HEMA/TMBDI
Performed polymer.
Well-mixed reaction vessel is added in 3000 grams of macromolecular polyether polyol 1 and is heated to 65 DEG C.Then it adds
HEMA/TMBDI performed polymer and ring zinc acetate catalyst (air chemical industry, 6g) simultaneously stir reaction mixture 2 hours at 75 DEG C,
Cooling obtains macromonomer 1, and degree of unsaturation is 0.055mol/kg after measured.
Embodiment 2
1) dimethyl diethyl succinonitrile adds hydrogen to prepare dimethyl diethyl butanediamine:
Referring to embodiment 1, tetramethyl fourth two is replaced using azobisisovaleronitrile decomposition product dimethyl diethyl succinonitrile
Nitrile.
2) dimethyl diethyl butanediamine prepares dimethyl diethyl fourth diisocyanate MEBDI:
Referring to embodiment 1, tetramethyl butane diamine is replaced using dimethyl diethyl butanediamine.
3) preparation of macromolecular polyether polyol 2:
Referring to embodiment 1, change material ratio, sorbierite/EO/PO mass ratio is 1.84/14.72/83.44, measurement
Hydroxyl value is about 34mgKOH/g.
4) preparation of macromonomer 2:
By the dimethyl diethyl fourth diisocyanate (MEBDI, 6.78g) of above-mentioned preparation, isooctyl acid bismuth catalyst (air
Chemical industry, 270mg) and hydroquinone (Rhodia, 20mg) be added in well-mixed reaction vessel and be heated to 40 DEG C.Then
Hydroxy-ethyl acrylate (HEA) 3.52g is added, and reaction mixture is stirred 2 hours, prepares HEA/MEBDI performed polymer.
Well-mixed reaction vessel is added in 300 grams of macromolecular polyether polyol 2 and is heated to 45 DEG C.Then it adds
The above-mentioned performed polymer of HEA/MEBDI and stannous octoate catalyst (air chemical industry, 300mg) simultaneously stir reaction mixture at 80 DEG C
It mixes 1 hour, cooling obtains macromonomer 2, and degree of unsaturation is 0.093mol/kg after measured.
Embodiment 3
1) dimethyl diisobutyl succinonitrile adds hydrogen to prepare dimethyl diisobutyl butanediamine:
Referring to embodiment 1, tetramethyl fourth is replaced using azobisisoheptonitrile decomposition product dimethyl diisobutyl succinonitrile
Dintrile.
2) dimethyl diisobutyl butanediamine prepares dimethyl diisobutyl fourth diisocyanate MPBDI:
Referring to embodiment 1, tetramethyl butane diamine is replaced using dimethyl diisobutyl butanediamine.
3) preparation of macromolecular polyether polyol 3:
Referring to embodiment 1, change material ratio, sorbierite/EO/PO mass ratio be 2.60/24.35/73.05 about
48mgKOH/g。
4) preparation of macromonomer 3:
Dimethyl diisobutyl fourth diisocyanate (self-produced, MPBDI, 11.98g), 4-methyl-diaminopropane catalyst is (empty
Gasify work, 600mg) and hydroquinone (Rhodia, 20mg) be added in well-mixed reaction vessel and be heated to 60 DEG C, so
Hydroxy propyl methacrylate (HPMA, commercially available, 6.16g) is added afterwards and stirs reaction mixture 1 hour, prepares HPMA/
MPBDI performed polymer.
Well-mixed reaction vessel is added in 300 grams of macromolecular polyether polyol 3 and is heated to 45 DEG C.Then addition is pre-
Aggressiveness and benzyl dimethylamine catalyst (air chemical industry, 150mg) simultaneously stir reaction mixture 3 hours at 60 DEG C, cool down
To macromonomer 3, degree of unsaturation is 0.121mol/kg after measured.
Embodiment 4
It is prepared by polymer polyatomic alcohol 1:
500ml four-hole bottle is equipped with blender, heating device, temperature control device and feeder as reactor.In reactor
Middle addition basic polyether 55.4g (Wan Hua3156), 4.7g macromonomer 1, after nitrogen displacement, stirring is slow
It is warming up to 110 DEG C, is continuously added to liftout (10.47g isopropanol, 85.71g basic polyether3156,46.55g third
Alkene nitrile, 69.83g styrene, 1.21g azodiisobutyronitrile mixed liquor), control 115 DEG C~120 DEG C of temperature.Drop in 100min
It adds complete, feeds intake and finish, aging reaction 1 hour, continue vacuum and take off list 2h, obtain product, measurement product index.Hydroxyl value
30.81mgKOH/g, admittedly contain 44.32%, viscosity 4815mPaS.
It collects decomposition product: after vacuum system air displacement, removing vacuum heat exchanger, discovery is in upper aggregation white knot
Eutectic substance, the careful collection crystalline material, as tetramethyl succinonitrile.The tetramethyl succinonitrile can be applied to the relaying of embodiment 1
It is continuous to prepare macromonomer 1.
Embodiment 5
It is prepared by polymer polyatomic alcohol 2:
500ml four-hole bottle is equipped with blender, heating device, temperature control device and feeder as reactor.In reactor
Middle addition basic polyether 55.4g (Wan Hua3156), 5.9g macromonomer 2, after nitrogen displacement, stirring is slow
It is warming up to 110 DEG C, is continuously added to liftout (10.47g isopropanol, 85.71g basic polyether3156,46.55g
Acrylonitrile, 69.83g styrene, 1.26g azobisisovaleronitrile mixed liquor), control 115 DEG C~120 DEG C of temperature.In 100min
It is added dropwise, feeds intake and finish, aging reaction 1 hour, continue vacuum and take off list 2h, obtain product, measure product index.Hydroxyl value
30.83mgKOH/g, admittedly contain 43.85%, viscosity 4453mPaS.
It collects decomposition product: after vacuum system air displacement, removing vacuum heat exchanger, discovery is in upper aggregation white knot
Eutectic substance, the careful collection crystalline material, as dimethyl diethyl succinonitrile.The dimethyl diethyl succinonitrile can be applied to
Continue to prepare macromonomer 2 in embodiment 1.
Embodiment 6
It is prepared by polymer polyatomic alcohol 3:
500ml four-hole bottle is equipped with blender, heating device, temperature control device and feeder as reactor.In reactor
Middle addition basic polyether 55.4g (Wan Hua3156), macromonomer 6.4g is stirred and is slowly risen after nitrogen displacement
110 DEG C of Wen Zhizhi, it is continuously added to liftout (10.47g isopropanol, 85.71g basic polyether3156,46.55g propylene
Nitrile, 69.83g styrene, 1.32g azobisisoheptonitrile mixed liquor), control 115 DEG C~120 DEG C of temperature.It is added dropwise in 100min
It finishes, feeds intake and finish, aging reaction 1 hour, continue vacuum and take off list 2h, obtain product, measure product index.Hydroxyl value
31.33mgKOH/g, admittedly contain 44.48%, viscosity 4319mPaS.
It collects decomposition product: after vacuum system air displacement, removing vacuum heat exchanger, discovery is in upper aggregation white knot
Eutectic substance, the careful collection crystalline material, as dimethyl diisobutyl succinonitrile.The dimethyl diisobutyl succinonitrile can answer
For continuing to prepare macromonomer 2 in embodiment 1.
Claims (18)
1. a kind of macromonomer with more alkyl structures, structure are as follows:
Wherein, R1、R2、R3、R4、R5And R6Separately indicate polyethylene oxide segment and/or polypropylene oxide segments；
R1、R2、R3、R4、R5And R6The weight ratio of polypropylene oxide segments summation and polyethylene oxide segment summation in 6 segments
It is 3~19；
R7、R8、R9And R10Separately indicate methyl, ethyl, isobutyl group；
R11Indicate H or methyl；
R12For-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)CH2Or-CH2(CH3)CH-。
2. with the macromonomer of more alkyl structures described in claim 1, which is characterized in that R7With R9Identical expression methyl, R8
With R10Identical expression methyl, ethyl or isobutyl group.
3. with the macromonomer of more alkyl structures described in claim 2, which is characterized in that R7、R8、R9And R10Identical expression
Methyl.
4. with the macromonomer preparation method of more alkyl structures described in claim 1, which is characterized in that including following step
It is rapid:
Diisocyanate reacts in the presence of catalyst c-1 with the hydroxy compounds containing double bond structure prepares performed polymer, performed polymer
React the macromonomer that preparation has more alkyl structures in the presence of catalyst c-2 with macromolecular polyether polyol again.
5. according to the method described in claim 4, it is characterized in that, the diisocyanate ester structure are as follows:
Wherein R7、R8、R9And R10Separately indicate methyl, ethyl, isobutyl group；
The hydroxy compounds containing double bond structure is selected from hydroxyethyl methacrylate, hydroxy propyl methacrylate, acrylic acid hydroxyl
One of ethyl ester and hydroxypropyl acrylate are a variety of；
The molar ratio of the diisocyanate and the hydroxy compounds containing double bond structure is 1/3~3/1.
6. according to the method described in claim 5, it is characterized in that, R7With R9Identical expression methyl, R8With R10Identical expression first
Base, ethyl, isobutyl group.
7. according to the method described in claim 6, it is characterized in that, R7、R8、R9And R10Identical expression methyl；
8. according to the method described in claim 5, it is characterized in that, the diisocyanate be tetramethyl fourth diisocyanate,
One of dimethyl diisobutyl fourth diisocyanate and dimethyl diethyl fourth diisocyanate are a variety of.
9. according to the method described in claim 4, it is characterized in that, the macromolecular polyether polyol structure is as follows:
Wherein R1、R2、R3、R4、R5And R6Separately indicate polyethylene oxide segment and/or polypropylene oxide segments；
The average weight-average molecular weight of segment is 1100~2800, and the average weight-average molecular weight of segment indicates R1、R2、R3、R4、R5And R6
Again divided by 6 after the weight average molecular weight adduction of 6 segments；
R1、R2、R3、R4、R5And R6The weight ratio of polypropylene oxide segments summation and polyethylene oxide segment summation in 6 segments
It is 19~3；
20~48mgKOH/g of the macromolecular polyether polyol hydroxyl value；
The molar ratio of the diisocyanate and macromolecular polyether polyol is 1/3~3/1.
10. according to the method described in claim 4, it is characterized in that, the diisocyanate and the hydroxylating containing double bond structure
Closing object and preparing the reaction temperature of performed polymer is 0~80 DEG C；Reaction time 0.1~5 hour；
The reaction temperature of the performed polymer and macromolecular polyether polyol is 40~100 DEG C；Reaction time 0.1~5 hour.
11. side described in any one of macromonomer or claim 4-10 described in claim 1-3 with more alkyl structures
The method that the macromonomer with more alkyl structures of method preparation prepares polymer polyatomic alcohol as raw material, including it is following
Step:
1) intermittently operated is used, the macromonomer with more alkyl structures is mixed with part basis polyether polyol as bottom material
Reaction kettle is added；
2) after heating bottom material, remaining basic polyether polyalcohol, chain-transferring agent, initiator, ethylenically unsaturated monomer compound are mixed
Cooperation is that liftout is continuously added to reaction kettle, and certain pressure and temperature is kept in reaction process, removes unreacted after being added dropwise
Monomer, chain-transferring agent and decomposition of initiator product, obtain polymer polyatomic alcohol.
12. according to the method for claim 11, which is characterized in that the initiator is selected from azodiisobutyronitrile, azo two
One of different heptonitrile, azobisisovaleronitrile are a variety of；By weight, the initiator amount is the pure and mild alkene of basic polyether polyols
Belong to the 0.3%~0.5% of unsaturated monomer compound gross mass.
13. according to the method for claim 11, which is characterized in that the ethylenically unsaturated monomer includes aliphatic conjugation two
Alkene, vinyl aromatic compounds, α, β-olefinically unsaturated nitriles, α, β-olefinic unsaturated amides, α, β-ethylenically unsaturated carboxylic acids, α,
In β-ethylenically unsaturated carboxylic acids ester, vinyl esters, vinyl ethers, vinyl ketone, vinyl halide and vinylidene halide
It is one or more；The mass ratio of the ethylenically unsaturated monomer and basic polyether polyalcohol is 0.1%-200%.
14. according to the method for claim 13, which is characterized in that the ethylenically unsaturated monomer includes vinyl aromatic
Close object and olefinically unsaturated nitriles；
15. according to the method for claim 14, which is characterized in that the ethylenically unsaturated monomer is styrene and propylene
Nitrile,
16. according to the method for claim 15, which is characterized in that the ethylenically unsaturated monomer be weight ratio 10: 90~
90: 10 styrene and acrylonitrile；
17. according to the method for claim 11, which is characterized in that the macromonomer with more alkyl structures is by weight
Meter, dosage are the 0.3%~10% of the pure and mild ethylenically unsaturated monomer compound gross mass of basic polyether polyols；
The mass ratio of basic polyether polyalcohol is 1/10-10/1 in step 1) and step 2).
18. according to the method for claim 11, which is characterized in that the temperature that bottom material heats in step 2) is 80~140 DEG C；
The reaction temperature of step 2) is 80~150 DEG C, and gauge pressure is 0~0.6Mpa.
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| US11795265B2 (en) | 2018-12-26 | 2023-10-24 | Wanhua Chemical Group Co., Ltd. | Macromonomeric stabilizer, preparation method thereof, and method for preparing polymeric polyol |
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