CN106242954A - The polyetheramine preparation method of low molecular polyether polyhydric alcohol - Google Patents
The polyetheramine preparation method of low molecular polyether polyhydric alcohol Download PDFInfo
- Publication number
- CN106242954A CN106242954A CN201610620498.0A CN201610620498A CN106242954A CN 106242954 A CN106242954 A CN 106242954A CN 201610620498 A CN201610620498 A CN 201610620498A CN 106242954 A CN106242954 A CN 106242954A
- Authority
- CN
- China
- Prior art keywords
- polyetheramine
- polyhydric alcohol
- low molecular
- preparation
- reaction
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
Abstract
The invention belongs to polyether polyol synthesis technical field, be specifically related to the preparation method of a kind of polyetheramine low molecular polyether polyhydric alcohol.Only with 2 methyl 1,3 propylene glycol for initiator, add base metal catalysts, first low temperature and epoxide reaction, then high temperature expoxy propane and block, to obtain final product.The present invention is in the polymerization, use 2 methyl 1,3 propylene glycol are as initiator, because the regularity of its structure and symmetry, as the activity of two ends, when with epoxide polymerization, polyether structure is more regular, when amine blocks, two ends activity is consistent, has the features such as amorphism, strong weatherability, stretch-proof, bending resistance are strong.This structure can make polyetheramine have low melting point, low viscosity, the feature good with auxiliary agent intersolubility.
Description
Technical field
The invention belongs to polyether polyol synthesis technical field, be specifically related to a kind of polyetheramine low molecular polyether polynary
The preparation method of alcohol.
Background technology
Polyetheramine be a class main chain be polyether polyol structure, end active functional group is the polymer of amido.Polyetheramine
It is that the ammonification at high temperature under high pressure of the polyether polyol by Polyethylene Glycol, polypropylene glycol or ethylene glycol/propylene glycol copolymers obtains
Arrive.Polyetheramine can be as the high-performance firming agent of epoxy resin, for producing the composite of high intensity, high tenacity；Tool
There is relatively low viscosity, when being applied to epoxide terrace or anticorrosive paint, it is possible to reduce solvent load, reduce system viscosity；As
The key component of polyurea materials, the water-proof system at xoncrete structures such as high-speed rail bridge, bridge spanning the sea, dam, large stadiums has
A lot of application examples, and show the performance of excellence etc..
Patent about polyetheramine is all the low molecular polyether polyhydric alcohol using traditional handicraft synthesis at present, by difference
Technique improve amine conversion ratio or improve amine number.And traditional handicraft synthesis low molecular weight polycaprolactone ethoxylated polyhydric alcohol, from GPC spectrogram (see
Fig. 1) upper it can be seen that molecular weight distribution width, and the situation at multiple miscellaneous peak occurs, prepare polyethers by such polyether polyol
Amine, amine ending ratio deviation low, active is big, unstable product quality.
Polyetheramine is amine end-blocking, and polyether polyol molecular weight different on main chain and the reaction of structure scalable polyetheramine
A series of performances such as activity, toughness, viscosity and hydrophilic, amido is provided that the possibility reacted to polyetheramine and multiple compounds
Property.Its special molecular structure imparts the combination property that polyetheramine is excellent.That is the structure of polyether polyol and quality
Directly determine application and the mechanical property of a series of performances such as the reactivity of polyetheramine, toughness, viscosity and hydrophilic
Index.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of polyetheramine low molecular polyether polyhydric alcohol, the polyethers of preparation
Polyhydric alcohol low-unsaturation-degree, narrower molecular weight distribution, can also make polyetheramine have more excellent serviceability simultaneously.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol of the present invention is only with 2-methyl isophthalic acid, 3-the third two
Alcohol is initiator, adds base metal catalysts, first low temperature and epoxide reaction, then high temperature expoxy propane and blocks, to obtain final product.
Described base metal catalysts is one or both in potassium hydroxide or sodium hydroxide, and consumption is 2-methyl isophthalic acid,
Ammediol, epoxide and the 0.3-0.5% of expoxy propane three's gross mass.
Described cryogenic temperature is 80-95 DEG C, and high-temperature temperature is 100-120 DEG C.
Described epoxide is one or both in expoxy propane or oxirane, and consumption is epoxide and epoxy
The 30-70% of propane gross mass.
Described 2-methyl-1,3-propanediol is 90:50-610 with the mass ratio of epoxide.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol of the present invention, step is as follows:
(1) low temperature polymerization reaction: add 2-methyl isophthalic acid, ammediol and base metal catalysts the most in a kettle., stir
After mixing uniformly, nitrogen is replaced 3-5 time, is evacuated to vacuum pressure≤-0.09MPa, stops evacuation, heats up, when temperature reaches 80 DEG C,
Then being continuously added to epoxide, carry out polyreaction, reaction temperature controls at 80-95 DEG C, and reaction pressure≤0.4MPa adds
After epoxide, continue reaction, wait after not changing 30 minutes to pressure stability, obtain intermediate polyether polyol；
(2) high temperature polymerization reaction: the intermediate polyether polyol heating that will obtain after low temperature polymerization, when temperature reaches 100
DEG C, then it being continuously added to expoxy propane, carry out polyreaction end-blocking, reaction temperature controls at 100-120 DEG C, reaction pressure≤
0.4MPa, after expoxy propane adds, continues reaction, waits after not changing 30 minutes to pressure stability, and evacuated pressure≤-
Under 0.09MPa, sloughing unreacted propylene oxide monomer, polyreaction completes；Then 90 DEG C it are cooled to, the product complete to polymerization
Thing adds phosphate aqueous solution and is neutralized reaction at 80-90 DEG C, adds adsorbent abjection potassium/sodium ion afterwards, and at Vacuum Pressure
It is dehydrated under power≤-0.09MPa, it is filtered, obtains required polyether polyol.
In low temperature polymerization reaction described in step (1), by controlling the quality of epoxide, gained intermediate polyethers is many
Unit's alcohol molecular weight control is at 140-700.
Phosphate aqueous solution described in step (2) be concentration be phosphoric acid and the mixture of distilled water of 85%, the phosphorus of 85%
Acid consumption is 2.3-2.6 times of base metal catalysts quality, and the consumption of distilled water is 2-methyl isophthalic acid, ammediol, epoxide
4-7% with expoxy propane three's gross mass.
Adsorbent described in step (2) is one or more in magnesium silicate, aluminium silicate or aluminium-magnesium silicate, and adsorbent is used
Amount is 2-methyl-1,3-propanediol, epoxide and the 0.31-0.45% of expoxy propane three's gross mass.
In high temperature polymerization reaction described in step (2), by controlling expoxy propane consumption, gained polyether polyol molecule
Amount controls at 200-1000.
Neutralizing described in step (2) reacts the amount by controlling phosphate aqueous solution, and gained polyether polyol PH controls
5.5-6.9；Vacuum dehydration makes polyether polyol moisture Control≤0.05%.
The present invention compared with prior art, has the advantages that
(1) present invention is in the polymerization, uses 2-methyl isophthalic acid, and ammediol is as initiator, because the rule of its structure
Whole property and symmetry, as the activity of two ends, when with epoxide polymerization, polyether structure is more regular, and when amine blocks, live in two ends
Property consistent, there is the features such as amorphism, strong weatherability, stretch-proof, bending resistance are strong.It is low that this structure can make polyetheramine have
Fusing point, low viscosity, the feature good with auxiliary agent intersolubility.
(2) two-stage process: the reaction of low temperature polymerization reaction, then back segment high temperature polymerization before this, can from GPC spectrogram (see Fig. 2)
To find out that such technique can make polyether polyol narrow molecular weight distribution, and being single-peak structure, more regular, quality is more stable.
(3) use epoxide polymerization in front end, make polyether polyol have different structures, it is provided that different performances.
Adding expoxy propane end-blocking in rear end, make polyether polyol two-end structure consistent, the activity at two ends is also consistent, so poly-in synthesis
During ether amines, two ends amination simultaneously, improves amine conversion ratio, improves amine number.
Accompanying drawing explanation
Fig. 1 is the GPC spectrogram of the low molecular polyether polyhydric alcohol of traditional handicraft synthesis.
Fig. 2 is the GPC spectrogram of the low molecular polyether polyhydric alcohol that the present invention synthesizes.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
In 2.5L autoclave, 2-methyl isophthalic acid, ammediol 270g, sodium hydroxide 2.4g, evacuation is added under room temperature
Replace 3 times to-0.09MPa nitrogen, start stirring and rise high-temperature to 80 DEG C, under vacuum is-0.09MPa, dripping continuously
Add 150g epoxide, its oxypropylene 30g, oxirane 120g.Reacting kettle inner pressure≤0.4MPa, reaction temperature is
At 80-95 DEG C, continue slaking reaction 1 hour after charging, obtain intermediate polyether polyol.Intensification is heated to 100 DEG C, so
Rear dropping 180g expoxy propane continuously, continues reaction a period of time, and reaction temperature controls at 100-120 DEG C, and reaction pressure≤
0.4MPa, waits after not changing 30 minutes to pressure stability, under evacuated pressure≤-0.09MPa, sloughs unreacted expoxy propane
Monomer, polyreaction completes.It is cooled to less than 90 DEG C, adds 5.52g phosphoric acid and the phosphate aqueous solution of 30g distilled water composition,
At 90 DEG C, stirring reaction 1 hour, it is subsequently adding 1.8g Magnesiumaluminumsilicate, stirs 40 minutes, under vacuum pressure≤-0.09MPa,
Vacuum dehydration 4h, obtains polyether polyol a after filtration.Concrete test data are shown in Table 1.
Embodiment 2
In 2.5L autoclave, add 2-methyl isophthalic acid, ammediol 360g, potassium hydroxide 8.32g under room temperature, take out true
Empty replace 3 times to-0.09MPa nitrogen, start stirring and rise high-temperature to 80 DEG C, under vacuum is-0.09MPa, continuously
Dropping 860g epoxide, its oxypropylene 420g, oxirane 420g.Reacting kettle inner pressure≤0.4MPa, reaction temperature
For at 80-95 DEG C, continue slaking reaction 1 hour after charging, obtain intermediate polyether polyol.Intensification is heated to 100 DEG C,
Dropping 860g expoxy propane the most continuously, continues reaction a period of time, and reaction temperature controls at 100-120 DEG C, and reaction pressure≤
0.4MPa, waits after not changing 30 minutes to pressure stability, under evacuated pressure≤-0.09MPa, sloughs unreacted expoxy propane
Monomer, polyreaction completes.It is cooled to less than 90 DEG C, adds 19.9g phosphoric acid and the phosphate aqueous solution of 104g distilled water composition,
At 90 DEG C, stirring reaction 1 hour, it is subsequently adding 7.28g magnesium silicate, stirs 40 minutes, under vacuum pressure≤-0.09MPa, very
Empty dehydration 3h, obtains polyether polyol b after filtration.Concrete test data are shown in Table 1.
Embodiment 3
In 2.5L autoclave, 2-methyl isophthalic acid, ammediol 180g, potassium hydroxide 8g, evacuation is added under room temperature
Replace 3 times to-0.09MPa nitrogen, start stirring and rise high-temperature to 80 DEG C, under vacuum is-0.09MPa, dripping continuously
Add 1229g epoxide, be all expoxy propane.Reacting kettle inner pressure≤0.4MPa, at reaction temperature is 80-95 DEG C, has fed
Continue slaking reaction 1 hour after Biing, obtain intermediate polyether polyol.Intensification is heated to 100 DEG C, the most continuously dropping 600g ring
Ethylene Oxide, continues reaction a period of time, and reaction temperature controls at 100-120 DEG C, and reaction pressure≤0.4MPa waits to pressure stability
After not changing 30 minutes, under evacuated pressure≤-0.09MPa, sloughing unreacted propylene oxide monomer, polyreaction completes.
Being cooled to less than 90 DEG C, add 19.2g phosphoric acid and the phosphate aqueous solution of 100g distilled water composition, at 90 DEG C, stirring reaction 1 is little
Time, it is subsequently adding 8g aluminium silicate, stirs 40 minutes, under vacuum pressure≤-0.09MPa, vacuum dehydration 3h, is gathered after filtration
Ethoxylated polyhydric alcohol c.Concrete test data are shown in Table 1.
Table 1 embodiment 1-3 prepares polyether polyol test index
Claims (10)
1. the polyetheramine preparation method of low molecular polyether polyhydric alcohol, it is characterised in that only with 2-methyl isophthalic acid, 3-the third two
Alcohol is initiator, adds base metal catalysts, first low temperature and epoxide reaction, then high temperature expoxy propane and blocks, to obtain final product.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol the most according to claim 1, it is characterised in that described
Base metal catalysts be one or both in potassium hydroxide or sodium hydroxide, consumption is 2-methyl isophthalic acid, ammediol, epoxy
Compound and the 0.3-0.5% of expoxy propane three's gross mass.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol the most according to claim 1, it is characterised in that described
Cryogenic temperature be 80-95 DEG C, high-temperature temperature is 100-120 DEG C.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol the most according to claim 1, it is characterised in that described
Epoxide be one or both in expoxy propane or oxirane, consumption is epoxide and expoxy propane gross mass
30-70%.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol the most according to claim 1, it is characterised in that described
The mass ratio of 2-methyl-1,3-propanediol and epoxide be 90:50-610.
6., according to the preparation method of the arbitrary described polyetheramine low molecular polyether polyhydric alcohol of claim 1-5, its feature exists
As follows in step:
(1) low temperature polymerization reaction: adding 2-methyl isophthalic acid, ammediol and base metal catalysts the most in a kettle., stirring is all
After even, nitrogen is replaced 3-5 time, is evacuated to vacuum pressure≤-0.09MPa, stops evacuation, heats up, when temperature reaches 80 DEG C, then
Being continuously added to epoxide, carry out polyreaction, reaction temperature controls at 80-95 DEG C, and reaction pressure≤0.4MPa adds epoxy
After compound, continue reaction, wait after not changing 30 minutes to pressure stability, obtain intermediate polyether polyol；
(2) high temperature polymerization reaction: the intermediate polyether polyol heating that will obtain after low temperature polymerization, when temperature reaches 100 DEG C, so
After be continuously added to expoxy propane, carry out polyreaction end-blocking, reaction temperature controls at 100-120 DEG C, reaction pressure≤0.4MPa,
After expoxy propane adds, continue reaction, wait after not changing 30 minutes to pressure stability, under evacuated pressure≤-0.09MPa, de-
Going unreacted propylene oxide monomer, polyreaction completes；Then it is cooled to 90 DEG C, the product that polymerization is complete is added phosphoric acid water
Solution is neutralized reaction at 80-90 DEG C, adds adsorbent abjection potassium/sodium ion afterwards, and at vacuum pressure≤-0.09MPa
Lower dehydration, filters it, obtains required polyether polyol.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol the most according to claim 6, it is characterised in that step
(1) the intermediate polyether polyol molecular weight control described in is at 140-700.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol the most according to claim 6, it is characterised in that step
(2) phosphate aqueous solution described in be concentration be phosphoric acid and the mixture of distilled water of 85%, the phosphoric acid consumption of 85% be alkali gold
2.3-2.6 times of metal catalyst quality, the consumption of distilled water is 2-methyl isophthalic acid, ammediol, epoxide and expoxy propane three
The 4-7% of person's gross mass.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol the most according to claim 6, it is characterised in that step
(2) adsorbent described in is one or more in magnesium silicate, aluminium silicate or aluminium-magnesium silicate, adsorbent amount be 2-methyl-
1,3-propylene glycol, epoxide and the 0.31-0.45% of expoxy propane three's gross mass.
The preparation method of polyetheramine low molecular polyether polyhydric alcohol the most according to claim 6, it is characterised in that step
(2) the polyether polyol molecular weight control described in is at 200-1000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610620498.0A CN106242954B (en) | 2016-08-01 | 2016-08-01 | The preparation method of polyetheramine low molecular polyether polyalcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610620498.0A CN106242954B (en) | 2016-08-01 | 2016-08-01 | The preparation method of polyetheramine low molecular polyether polyalcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106242954A true CN106242954A (en) | 2016-12-21 |
| CN106242954B CN106242954B (en) | 2019-03-15 |
Family
ID=57605709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610620498.0A Active CN106242954B (en) | 2016-08-01 | 2016-08-01 | The preparation method of polyetheramine low molecular polyether polyalcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106242954B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437725A (en) * | 2019-08-14 | 2019-11-12 | 四川暄洋新材料科技有限公司 | It is a kind of to pass through silicate modified polyetheramine polyurethane antifouling paint and its application |
| CN111057228A (en) * | 2019-12-13 | 2020-04-24 | 张家港美景荣化学工业有限公司 | Preparation method of low molecular weight polyether polyol |
| CN114316252A (en) * | 2021-12-10 | 2022-04-12 | 湖北三江航天江河化工科技有限公司 | Telechelic rapid thermal/photo-curing ablation-resistant resin and synthetic method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110991A (en) * | 1991-04-01 | 1992-05-05 | Texaco Chemical Company | Heterogeneous catalyst for alkoxylation of alcohols |
| WO1997003169A1 (en) * | 1995-07-11 | 1997-01-30 | The Procter & Gamble Company | Concentrated, stable fabric softening composition |
| JP2005350402A (en) * | 2004-06-11 | 2005-12-22 | Sanyo Chem Ind Ltd | Monohydric alcohol alkylene oxide adduct and method for producing the same |
| WO2012010844A1 (en) * | 2010-07-23 | 2012-01-26 | Christopher Wickham Noakes | Production process for polyol for use in low ball rebound polyurethane foams |
| CN102516522A (en) * | 2011-12-15 | 2012-06-27 | 福建湄洲湾氯碱工业有限公司 | Method for synthesizing glyceryl polyether for pesticide emulsification |
| CN102875783A (en) * | 2011-07-15 | 2013-01-16 | 东丽纤维研究所（中国）有限公司 | Polyester and preparation method and usage thereof |
| CN103709392A (en) * | 2013-11-28 | 2014-04-09 | 山东蓝星东大化工有限责任公司 | Preparation method of polyether polyol for automobile sealant |
| CN104961888A (en) * | 2015-06-11 | 2015-10-07 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol for slow rebound foam |
-
2016
- 2016-08-01 CN CN201610620498.0A patent/CN106242954B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110991A (en) * | 1991-04-01 | 1992-05-05 | Texaco Chemical Company | Heterogeneous catalyst for alkoxylation of alcohols |
| WO1997003169A1 (en) * | 1995-07-11 | 1997-01-30 | The Procter & Gamble Company | Concentrated, stable fabric softening composition |
| JP2005350402A (en) * | 2004-06-11 | 2005-12-22 | Sanyo Chem Ind Ltd | Monohydric alcohol alkylene oxide adduct and method for producing the same |
| WO2012010844A1 (en) * | 2010-07-23 | 2012-01-26 | Christopher Wickham Noakes | Production process for polyol for use in low ball rebound polyurethane foams |
| CN102875783A (en) * | 2011-07-15 | 2013-01-16 | 东丽纤维研究所（中国）有限公司 | Polyester and preparation method and usage thereof |
| CN102516522A (en) * | 2011-12-15 | 2012-06-27 | 福建湄洲湾氯碱工业有限公司 | Method for synthesizing glyceryl polyether for pesticide emulsification |
| CN103709392A (en) * | 2013-11-28 | 2014-04-09 | 山东蓝星东大化工有限责任公司 | Preparation method of polyether polyol for automobile sealant |
| CN104961888A (en) * | 2015-06-11 | 2015-10-07 | 山东一诺威新材料有限公司 | Preparation method of polyether polyol for slow rebound foam |
Non-Patent Citations (2)
| Title |
|---|
| 刘小会等: "聚合工艺对低不饱和度高相对分子质量聚醚性能的影响", 《聚氨酯工业》 * |
| 王强等: "聚醚多元醇生产工艺控制的探讨", 《化工中间体》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437725A (en) * | 2019-08-14 | 2019-11-12 | 四川暄洋新材料科技有限公司 | It is a kind of to pass through silicate modified polyetheramine polyurethane antifouling paint and its application |
| CN111057228A (en) * | 2019-12-13 | 2020-04-24 | 张家港美景荣化学工业有限公司 | Preparation method of low molecular weight polyether polyol |
| CN114316252A (en) * | 2021-12-10 | 2022-04-12 | 湖北三江航天江河化工科技有限公司 | Telechelic rapid thermal/photo-curing ablation-resistant resin and synthetic method thereof |
| CN114316252B (en) * | 2021-12-10 | 2023-05-02 | 湖北三江航天江河化工科技有限公司 | Telechelic type rapid thermal/photo-curing ablation-resistant resin and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106242954B (en) | 2019-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103183793B (en) | Synthetic method of polycarboxylic acid type highly slump loss resistant water-reducing agent | |
| CN106242954A (en) | The polyetheramine preparation method of low molecular polyether polyhydric alcohol | |
| CN102492149B (en) | Preparation method of nonionic aqueous epoxy resin curing agent | |
| CN107936240B (en) | Preparation method of polyether macromonomer for polycarboxylate superplasticizer | |
| CN100463872C (en) | Preparation method of polycarboxylate water reducing agent | |
| US11639418B2 (en) | Synthesis process for one-step production of monomeric polyether for polycarboxylic acid water reducing agents | |
| CN105906753A (en) | Preparation method of polycarboxylate superplasticizer | |
| CN105330830A (en) | Terminal alkenyl nonsaturated polyether and purpose thereof | |
| CN106008953A (en) | Preparation method of low unsaturation degree and high intersolubility high molecular weight polyether polyol | |
| CN104628959A (en) | Method for synthesizing cement dispersing agent by using terminated functional polyethylene fatty acid ester macromonomer | |
| CN108623756A (en) | Special polycarboxylate water-reducer of ultra-high performance concrete and preparation method thereof | |
| CN105315452B (en) | The preparation method of soluble polyurethane grouting material PPG | |
| CN102718427B (en) | Sulfonyl modified carboxylic acid water-reducing agent and preparation method thereof | |
| CN103881082B (en) | The preparation method of polycarboxylic acid water reducer macromer methyl allyl alcohol polyoxyethylene ether | |
| CN101386489B (en) | Polycarboxylate dehydragent and preparation method thereof | |
| CN102503221A (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| CN104250375B (en) | disproportionated rosin amine polyoxyethylene polyoxypropylene ether and preparation method thereof | |
| CN102164973B (en) | Vinyloxy group-containing vinyl polymer | |
| CN107011191B (en) | Produce N, the method for N- dimethyldiglycolamine co-production N, N- dimethylethanolamine | |
| CN105399939A (en) | A synthetic method of cumenyl polyoxyethylene ether | |
| CN104211850B (en) | A kind of comb-shaped polymer containing reversible hydrogen bond and preparation method thereof | |
| CN111423323B (en) | Acifman ester and preparation method thereof | |
| US20160107935A1 (en) | Liquid dispersant composition for gypsum | |
| CN104086765B (en) | The preparation method of aliphatics coating polyether glycol | |
| CN107352835B (en) | High-performance antifreezing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: Linzi District of Shandong Province Jin Shan Zhen Feng Guan Lu 255400 Zibo City No. 58 Applicant after: SHANDONG INOV NEW MATERIAL CO., LTD. Address before: 255400 Shandong Province, Zibo city Linzi District South East Nanshan Road West five by ethylene Applicant before: SHANDONG INOV NEW MATERIAL CO., LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |