CN1629133A - Process for preparing quarternary ammonium salt compounds - Google Patents
Process for preparing quarternary ammonium salt compounds Download PDFInfo
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- CN1629133A CN1629133A CN 200410041871 CN200410041871A CN1629133A CN 1629133 A CN1629133 A CN 1629133A CN 200410041871 CN200410041871 CN 200410041871 CN 200410041871 A CN200410041871 A CN 200410041871A CN 1629133 A CN1629133 A CN 1629133A
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- ammonium salt
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Abstract
The invention provides a process for preparing quarternary ammonium salt compounds by using organic amine, organic acid and epoxy compound as raw material with the mol ratio of 1 : (0.80-1.0) : (1.2-1.8), charging 20-80% of overall material weight of water into the autoclave, charging organic acid with closed conduit, charging organic amine while stirring, controlling the reaction temperature between 70-120 deg. C, the pressure < 0.5 MPa, thermal insulating 1.0-2.0 hours at 90-120 deg. C, and dehydrating under subatmospheric pressure at the temperature of 90-120 deg. C.
Description
Technical field:
The present invention relates to a kind of preparation method of quaternary ammonium salt compound.
(2) background technology
Polyurethane foamed material normally is synthesized into by polyether glycol and the reaction of isocyanic ester chemistry, simultaneously with foamable reaction and gel reaction, can be controlled by catalyzer in the reaction process.In the rigid foam field, adopt two-dimethyl amine benzyl ethyl ether, pentamethyl-diethylenetriamine, the foamable reaction of tertiary amine catalyst may command urethane such as tetramethyl butane diamine; Adopt the gel reaction of catalyzer may command reactions such as triethylene diamine, dimethyl benzylamine, dimethyl ethylenimine, organotin; The polyurethane foam that processability is good must control foaming and gel reaction.
As everyone knows, the raw material of polyurethane foam---isocyanic ester not only can react with active dydrogen compounds, and can react with self.Discovered in recent years, the speed of the id reaction ability of isocyanic ester, be control foam late phase reaction speed principal element.And that the catalyzer that promotes the id reaction ability of isocyanic ester has is multiple, as metallic salt, hexahydrotriazine, quaternary ammonium salts etc.Wherein use quaternary ammonium salts catalyzer advantage more obvious, it have reaction temperature and, the characteristics little to processing performances such as bubble mobility influences.This is because it is less to reaction effect in earlier stage, and is very big to prescription later stage performance impact.In a word, the quaternary ammonium salts catalyzer can significantly be accelerated the foamy solidification rate, makes the foam demoulding easy to crack soon and not, thereby improves production efficiency of products.
At present, external major company is as such catalyzer such as TMR series product that U.S.'s gas companies is produced, better performances and stable, but the production technique of the said firm is also not known.The domestic patent documentation report that does not still have this respect, present domestic like product is because acid number is higher, and active ingredient content is lower, does not also apply.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of quaternary ammonium salt compound, its preparation technology is simple, and the gained quaternary ammonium salt compound has as the high-performance of producing the hard polyurethane foam catalyzer.
The method of the synthetic quaternary amine of the present invention is a raw material with Compound I, Compound I I and compound III, wherein:
Compound I is the organic amine that contains following general formula:
R
1, R
2, R
3Independently be selected from C respectively
1～C
10A kind of in straight chained alkyl or cyclohexyl, the phenyl;
Compound I is preferably Trimethylamine 99, triethylamine.
Compound I I is the organic acid that contains following general formula:
R is selected from H or C
1～C
10Straight chain alkane or branched-chain alkyl;
Compound I I is preferably formic acid, acetate, propionic acid, butyric acid, caproic acid, sad or isocaprylic acid;
Compound III is the epoxide that contains following general formula:
Rn is selected from: H, methyl or ethyl;
The present invention is medium with water, is undertaken by following reaction formula:
Operation as follows:
Reactor is taken out negative pressure and is used N
2Air in the displacement still, add deionized water, to in reactor, add the Compound I I that measures with closed conduit, stir adding Compound I down, 50 ℃ of control reaction temperature ∠, react after 20～60 minutes, slowly add compound III, and 70～120 ℃ of control reaction temperature (preferred 80～100 ℃), pressure ∠ 0.5Mpa, 90-120 ℃ is incubated 1.0～2.0 hours down, it is reacted completely; In 90～120 ℃ (being preferably 105-115 ℃) down negative pressure dehydration, water weight percentage 1～4% in the resultant to the still; The feeding quantity mol ratio of above Compound I, II, III is 1: (0.80～1.0): (1.2～1.8), the add-on of water are 20～80% of total weight of material.
Building-up reactions of the present invention is medium with water, and water consumption directly influences the production operation of product, and the water yield react comparatively steady, but the required energy consumption of dewatering is higher more for a long time; The water yield is less, the then difficult control of reaction process.
The present invention adopts the suitable water yield, makes reaction conditions extremely gentle, operates very simply, and reaction time is shorter.In the aqueous solution, the salt that the reaction of organic acid and organic amine generates becomes ionized state, and when epoxide joins in this reaction soln, it can combine and be the electron deficiency state with amine.The hydroxyl of product has certain influence to the performance of product, and the epoxide add-on is directly relevant with the hydroxyl value of product, so the add-on of gate ring oxide compound of the present invention; In addition, organic amine and organic acid ratio have direct influence to the acid number of product, and the present invention adopts suitable mol ratio, can guarantee product stability.
Embodiment
The preparation of embodiment 1 quaternary ammonium salt compound
The reactor water cleans, and takes out negative pressure and feeds N
2Air in the displacement still; Add deionized water 350g, the formic acid meter 250g with metering is pressed in the reactor by closed conduit, stirs to make material even, uses closed pipeline to add Trimethylamine 99 360g, and reacting kettle jacketing leads to water coolant, 15～50 ℃ of control reaction temperature; After Trimethylamine 99 added, 80～100 ℃ of temperature of reaction kettle, pressure slowly fed gauge rings Ethylene Oxide 550g less than under the 0.5MPa; Be incubated 1.0～2.0 hours, temperature is controlled at 85～95 ℃; Be warming up to 105～115 ℃ then with reactor decompression 1.0～2.0 hours; Sampling analysis, the moisture content that makes target product are 3.2%, acid number is that 4.2mgKOH/g, hydroxyl value are 450mgKOH/g.
Attached embodiment 2
The quaternary ammonium salts catalyzer that present method is produced is to the influence of hard polyurethane foam production technique
Admixtured polyether polyvalent alcohol and catalyzer, whipping agent weighing are poured in the stainless steel cup of 800ml, be pre-mixed evenly, again isocyanic ester is measured, pour in the stainless steel cup of 800ml, and stir, carry out foamable reaction, the parameter of observing response process different steps, parameter comprises cream time, fiber time, not sticking time, after the foam-formed slaking, surveys foamy and freely rises density.
For the practical situation of simulation foam production, promptly produce moulded foam, in aluminium-making mould, foam, make the pressurized foam, the demoulding in the corresponding time detects the foamy rate of expansion, characterizes the foamy curing speed.
Be convenient below test, the quaternary ammonium salt compound called after A that embodiment 1 is made.
Present embodiment is produced hard polyurethane foam with two kinds of proportion schemes, and wherein scheme 1
*Middle catalyzer C5 and the C8 of adopting do not adopt quaternary ammonium salt compound to make catalyzer, scheme 2
*In reduce the amount of C8, and added quaternary ammonium salt compound A.Below two kinds of scheme correlation test data are listed in the following table 1.The raw material of the adding of two kinds of schemes and catalyst component and consumption (weight part) are listed in the top of table 1, and reaction parameter is listed in the bottom of table.
In the table 1, C5, C8 belong to the product of U.S.'s gas companies; A is the quaternary ammonium salt compound catalyzer that the present invention makes, and suds-stabilizing agent B8404 is the product of German Gao Shi Mitt USA Corporation; Blowing agent H CFC141b is the product of Fu Shite company, and isocyanic ester is the product of the German Bayer company that adopts.
Table 1
| The raw material of production polyurethane foam and catalyzer | Scheme 1 * | Scheme 2 * |
| The admixtured polyether polyvalent alcohol | 100 | ?100 |
| Catalyzer C5 | 0.3 | ?0.3 |
| Catalyzer C8 | 2.2 | ?1.8 |
| Catalyst A | / | ?0.35 |
| Suds-stabilizing agent B8404 | 2 | ?2 |
| Blowing agent H CFC141b | 30 | ?30 |
| Isocyanate index | 110 | ?110 |
| Reaction parameter | ||
| Cream time, second | 8 | ?8 |
| The fiber time, second | 75 | ?74 |
| The not sticking time, second | 102 | ?100 |
| Freely rise density, kg/m 3 | 26.0 | ?26.2 |
| In 300 * 450 * 80 mould, foam | ||
| The demoulding in 8 minutes, slit foam | Cracking | Expansion 2.8mm |
| The demoulding in 10 minutes, slit foam | Expansion 3.2mm | Expansion 1.1mm |
As known from Table 1, scheme 2
*The sticking time shorten, foam curing speed is higher than scheme 1
*, the demoulding in 8 minutes is expanded and is not ftractureed, and scheme 1
*At the demoulding in 8 minutes cracking, the demoulding in 10 minutes is expanded still greater than scheme 1
*Expand the demoulding in 8 minutes, so aspect demolding performace, scheme 2
*Faster than scheme 1
*Meter clock more than 2 minutes.
Claims (4)
1. the preparation method of quaternary ammonium salt compound is characterized in that with Compound I, Compound I I and Compound I lI be raw material, wherein:
Compound I is the organic amine that contains following general formula:
R
1, R
2, R
3Independently be selected from C respectively
1～C
10A kind of in straight chained alkyl or cyclohexyl, the phenyl;
Compound I I is the organic acid that contains following general formula:
R is selected from H or C
1～C
10Straight chain alkane or branched-chain alkyl;
Compound III is the epoxide that contains following general formula:
Rn is selected from H, methyl or ethyl;
The feeding quantity mol ratio of above Compound I, II, III is 1: (0.80～1.0): (1.2～1.8),
Preparation process is as follows:
Reactor is taken out negative pressure and is used N
2Air in the displacement still adds deionized water, and the add-on of water is 20～80% of total weight of material; The Compound I I that in reactor, adds metering with closed conduit, stir and add Compound I down, 50 ℃ of control reaction temperature ∠, react after 20～60 minutes, slowly add compound III, and 70～120 ℃ of control reaction temperature, pressure ∠ 0.5Mpa, 90-120 ℃ is incubated 1.0～2.0 hours down, it is reacted completely; 90～120 ℃ of following negative pressure dehydrations, water weight percentage 1～4% in the resultant to the still.
2. the preparation method of quaternary ammonium salt compound according to claim 1 is characterized in that said Compound I is Trimethylamine 99 or triethylamine.
3. the preparation method of quaternary ammonium salt compound according to claim 1 is characterized in that said Compound I I is formic acid, acetate, propionic acid, butyric acid, caproic acid, sad or isocaprylic acid.
4. the preparation method of quaternary ammonium salt compound according to claim 1, after it is characterized in that adding compound III, temperature of reaction is controlled at 80～100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410041871 CN1629133A (en) | 2004-09-06 | 2004-09-06 | Process for preparing quarternary ammonium salt compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410041871 CN1629133A (en) | 2004-09-06 | 2004-09-06 | Process for preparing quarternary ammonium salt compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1629133A true CN1629133A (en) | 2005-06-22 |
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ID=34845924
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410041871 Pending CN1629133A (en) | 2004-09-06 | 2004-09-06 | Process for preparing quarternary ammonium salt compounds |
Country Status (1)
| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820302A (en) * | 2016-04-30 | 2016-08-03 | 华南理工大学 | Nonionic and anionic mixed waterborne polyurethane curing agent and preparation method thereof |
-
2004
- 2004-09-06 CN CN 200410041871 patent/CN1629133A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820302A (en) * | 2016-04-30 | 2016-08-03 | 华南理工大学 | Nonionic and anionic mixed waterborne polyurethane curing agent and preparation method thereof |
| CN105820302B (en) * | 2016-04-30 | 2018-09-14 | 华南理工大学 | A kind of nonionic and the mixed and modified water-based polyurethane curing agent of anion and preparation method thereof |
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