An acetylenic diol compound, a preparation method and application thereof

Abstract

The application discloses an acetylene diol compound and a preparation method and application thereof, and comprises the following steps: step one, acetylene diol monomers and caprolactone monomers are added into a reaction kettle, and nitrogen is introduced as a protective gas; step two, the temperature of the reaction kettle is increased to 40-60 DEG C, and a vacuum pump is opened to remove water; step three, after dehydration is completed, a catalyst is added, and the temperature is increased to a reaction temperature; after the temperature is increased, the reaction kettle is slowly introduced with an ethylene oxide monomer, and the pressure of the reaction is controlled; step four, after the reaction is completed, the vacuum pump is opened to perform vacuum devolatilization for 1-2 hours, and finally, the product is obtained after cooling and discharging, thereby the surfactant of the application has better high-temperature resistance and acid and alkali resistance than general acetylene diol polyether surfactants, has a wide application range, is non-toxic and can be degraded, can be quickly degraded even if discharged into the environment, is very friendly to the environment, and has a low surface tension.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemistry, and particularly relates to acetylene diol compounds and a preparation method and application thereof. BACKGROUND

[0002] A surfactant refers to a substance capable of significantly reducing the surface tension of a target solution, and has a fixed hydrophilic and lipophilic group which can be arranged in a direction on the surface of the solution. The surfactant has a series of physical and chemical effects such as wetting or anti-sticking, emulsification or demulsification, foaming or defoaming, and solubilization, dispersion, washing, corrosion prevention, and anti-static.

[0003] There are various types of surfactants, and the functions and application fields are different. Acetylene alcohol surfactants, also known as acetylene diol surfactants, have strong polarity and hydrophilicity due to the -C≡C- and -OH groups in the acetylene diol molecules, and the hydrophobicity is brought by the hydrocarbon group, which makes the acetylene diol become a non-ionic surfactant with excellent performance.

[0004] However, most of the acetylene diol compounds on the market are acetylene diol polyether surfactants formed by copolymerization of acetylene diol and ethylene oxide, propylene oxide. However, due to the presence of a large number of ether bonds, this type of surfactant is not resistant to high temperature, and is easily inactivated or has reduced surface activity in some high-temperature application environments such as plastic cleaning, industrial cleaning, and oil exploitation. In addition, the cloud point of this type of surfactant is low, and it will precipitate or partially precipitate at a higher temperature, thereby affecting the surface activity. Although the acetylene diol fluorine-containing polyether surfactant has strong chemical and thermal stability and excellent high-temperature resistance, it is difficult to degrade and has toxicity when discharged into the environment, which can cause great harm to human health. Although the silicon-containing acetylene diol compound is non-toxic, it has high cost and high price, and the ability of the silicon-containing acetylene diol compound to reduce surface tension does not have obvious advantages compared with other organic silicon surfactants.

[0005] In view of the above technical problems, there is an urgent need for a surfactant with high cloud point, good high-temperature resistance, low surface tension, and environmental friendliness. SUMMARY

[0006] To solve the above problems, the present application discloses an acetylene diol compound and a preparation method and application thereof.

[0007] To achieve the above-mentioned purposes, the technical scheme of the present application is as follows:

[0008] An acetylene diol compound, the chemical structural formula of the acetylene diol compound is as follows:

[0009]

[0010] wherein, R1, R2, R3 and R4 are H or alkyl

[0011] n and p are both the number of ethylene oxide, n+p is in the range of 10-25;

[0012] m and q are both the number of caprolactone, m+q is in the range of 5-20.

[0013] A preparation method of acetylene glycol compound, comprising the following steps:

[0014] Step one, acetylene glycol monomer and caprolactone monomer are added into a reaction kettle, and nitrogen is introduced as a protective gas;

[0015] Step two, the temperature of the reaction kettle is increased to 40-60℃, and a vacuum pump is opened for dehydration;

[0016] Step three, after dehydration, a catalyst is added to start heating to the reaction temperature, and after heating is completed, acetylene glycol monomer is slowly introduced into the reaction kettle to control the pressure of the reaction;

[0017] Step four, after the reaction is completed, the vacuum pump is opened for vacuum devolatilization for 1-2h, and finally the material is cooled and discharged to obtain the acetylene glycol compound of claim 1.

[0018] Further improvement, in the step one, the acetylene glycol monomer is one of 2-butyne-1,4-diol, 2,5-dimethylhexyne diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.

[0019] Further improvement, the acetylene glycol monomer is 2-butyne-1,4-diol.

[0020] Further improvement, in the step one, the mass ratio of acetylene glycol monomer and caprolactone monomer is 86-254:570-2280.

[0021] Further improvement, the catalyst is one or more of stannous octoate, stannous isooctoate, dibutyltin dilaurate, tetrabutyl titanate, preferably tetrabutyl titanate, and the mass ratio of acetylene glycol monomer to catalyst is 86-254:0.08768-0.22448.

[0022] Further improvement, the mass ratio of acetylene glycol monomer to ethylene oxide monomer is 86-254:440-1100.

[0023] Further improvement, in the step three, the reaction temperature is 120℃-160℃, preferably 140℃, and the reaction pressure is 0.2-1.2Mpa, preferably 0.6Mpa.

[0024] Use of an acetylenic diol compound as described above as a surfactant.

[0025] Advantages of the present application:

[0026] 1. Generally, the cloud point of surfactants will decrease with the increase of the number of hydrophobic chain segments, but the present application uses PCL segments as the hydrophobic chain segments of surfactants, because the PCL segments contain ester bonds, and the ester bonds belong to polar structures, which lead to the formation of hydrogen bonds between the ester bond-containing moieties and water, and the PCL segments and PEO segments are linear structures without steric hindrance, which are also easy to form hydrogen bonds with water. Within a certain range of water solubility, the interaction between the two will increase the cloud point of the surfactants of the present application, thereby increasing the temperature use range of the surfactants. In addition, the heat resistance and acid and alkali resistance of ester groups are superior to those of ether groups, so the surfactants of the present application have superior high-temperature resistance and acid and alkali resistance to general acetylenic diol polyether surfactants, and have a wider range of applications.

[0027] 2. The polycaprolactone segments and polyethylene oxide segments in the present application are also biodegradable, so the surfactants of the present application are non-toxic and can be degraded, and even if they are discharged into the environment, they can be quickly degraded, which is very friendly to the environment.

[0028] 3. The present application uses PCL segments as hydrophobic segments and PEO segments as hydrophilic segments to jointly regulate the hydrophilic-lipophilic balance of surfactants. Since the PCL segments and PEO segments are linear structures, this structure is conducive to the formation of a tight monolayer at the interface, reducing the intermolecular gap, thereby facilitating the formation of micelles and the close arrangement of the interface, and the synthesized surfactants have low surface tension and good surface activity. DETAILED DESCRIPTION

[0029] The present application is further illustrated below in conjunction with examples.

[0030] Example 1

[0031] (1) 86g of 2-butyne-1,4-diol and 570g of caprolactone monomer were added to a reaction kettle, nitrogen was introduced, and nitrogen was used as a protective gas for three times.

[0032] (2) The temperature was raised to 60℃, and the vacuum pump was opened for 1h of dehydration.

[0033] (3) After dehydration, the vacuum was broken with nitrogen, then 0.088g of tetrabutyl titanate catalyst was added, and the temperature was raised to 140℃. After the temperature was raised, 440g of ethylene oxide monomer was slowly introduced into the reaction kettle within 5h, and the pressure of the reaction was controlled at 0.6Mpa

[0034] (4) After the reaction is completed, the vacuum pump is opened at this temperature for vacuum devolatilization for 1.5 h, and finally the product is discharged after cooling to obtain the acetylenic diol surfactant. The GPC number average molecular weight is shown in Table 1.

[0035] Example 2

[0036] (1) 86 g of 2-butyne-1, 4-diol and 1140 g of caprolactone monomer are added into a reaction kettle, nitrogen is introduced, and nitrogen is replaced three times as a protective gas.

[0037] (2) The temperature is raised to 60°C, and the vacuum pump is opened for dehydration for 1 h.

[0038] (3) After the dehydration is completed, the vacuum is broken with nitrogen, then 0.133 g of tetrabutyl titanate catalyst is added to start heating to 140°C, after the heating is completed, 440 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 5 h, and the pressure of the reaction is controlled at 0.6 Mpa.

[0039] (4) After the reaction is completed, the vacuum pump is opened at this temperature for vacuum devolatilization for 1.5 h, and finally the product is discharged after cooling to obtain the acetylenic diol surfactant. The GPC number average molecular weight is shown in Table 1.

[0040] Example 3

[0041] (1) 86 g of 2-butyne-1, 4-diol and 1710 g of caprolactone monomer are added into a reaction kettle, nitrogen is introduced, and nitrogen is replaced three times as a protective gas.

[0042] (2) The temperature is raised to 60°C, and the vacuum pump is opened for dehydration for 1 h.

[0043] (3) After the dehydration is completed, the vacuum is broken with nitrogen, then 0.178 g of tetrabutyl titanate catalyst is added to start heating to 140°C, after the heating is completed, 440 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 6 h, and the pressure of the reaction is controlled at 0.6 Mpa.

[0044] (4) After the reaction is completed, the vacuum pump is opened at this temperature for vacuum devolatilization for 1.5 h, and finally the product is discharged after cooling to obtain the acetylenic diol surfactant. The GPC number average molecular weight is shown in Table 1.

[0045] Example 4

[0046] (1) 86 g of 2-butyne-1, 4-diol and 2280 g of caprolactone monomer are added into a reaction kettle, nitrogen is introduced, and nitrogen is replaced three times as a protective gas.

[0047] (2) The temperature is raised to 60°C, and the vacuum pump is opened for dehydration for 1 h.

[0048] (3) After the dehydration is completed, the vacuum is broken with nitrogen, then 0.225 g of tetrabutyl titanate catalyst is added to start warming to 140°C, after the warming is completed, 440 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 7 h, and the pressure of the reaction is controlled to be 0.6 Mpa.

[0049] (4) After the reaction is completed, the vacuum pump is opened at the temperature to perform vacuum devolatilization for 1.5 h, and finally the product is cooled and discharged to prepare the acetylenic diol surfactant, and the number average molecular weight of GPC is shown in Table 1.

[0050] Example 5

[0051] (1) 86 g of 2-butyne-1,4-diol and 1140 g of caprolactone monomer are added into a reaction kettle, nitrogen is introduced, and the nitrogen is replaced three times and used as a protective gas.

[0052] (2) The temperature is raised to 60°C, and the vacuum pump is opened to perform dehydration for 1 h.

[0053] (3) After the dehydration is completed, the vacuum is broken with nitrogen, then 0.15 g of tetrabutyl titanate catalyst is added to start warming to 140°C, after the warming is completed, 660 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 6 h, and the pressure of the reaction is controlled to be 0.6 Mpa.

[0054] (4) After the reaction is completed, the vacuum pump is opened at the temperature to perform vacuum devolatilization for 1.5 h, and finally the product is cooled and discharged to prepare the acetylenic diol surfactant, and the number average molecular weight of GPC is shown in Table 1.

[0055] Example 6

[0056] (1) 86 g of 2-butyne-1,4-diol and 1140 g of caprolactone monomer are added into a reaction kettle, nitrogen is introduced, and the nitrogen is replaced three times and used as a protective gas.

[0057] (2) The temperature is raised to 60°C, and the vacuum pump is opened to perform dehydration for 1 h.

[0058] (3) After the dehydration is completed, the vacuum is broken with nitrogen, then 0.168 g of tetrabutyl titanate catalyst is added to start warming to 140°C, after the warming is completed, 880 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 7 h, and the pressure of the reaction is controlled to be 0.6 Mpa.

[0059] (4) After the reaction is completed, the vacuum pump is opened at the temperature to perform vacuum devolatilization for 1.5 h, and finally the product is cooled and discharged to prepare the acetylenic diol surfactant, and the number average molecular weight of GPC is shown in Table 1.

[0060] Example 7

[0061] (1) Put 86 g 2-butyne-1, 4-diol and 1140 g caprolactone monomer into the reactor, and replace with nitrogen three times and as a protective gas.

[0062] (2) Increase the temperature to 60°C, and open the vacuum pump for dehydration for 1 h.

[0063] (3) After dehydration, break the vacuum with nitrogen, then add 0.186 g tetrabutyl titanate catalyst to start heating to 140°C, and after heating, slowly introduce 1100 g ethylene oxide monomer into the reactor within 7 h, and control the reaction pressure at 0.6 MPa.

[0064] (4) After the reaction is completed, open the vacuum pump at this temperature for vacuum devolatilization for 1.5 h, and finally cool and discharge to obtain the acetylenic diol surfactant, and the GPC number average molecular weight is shown in Table 1.

[0065] Example 8

[0066] (1) Put 142 g 2, 5-dimethyl hexyne diol and 1140 g caprolactone monomer into the reactor, and replace with nitrogen three times and as a protective gas.

[0067] (2) Increase the temperature to 60°C, and open the vacuum pump for dehydration for 1 h.

[0068] (3) After dehydration, break the vacuum with nitrogen, then add 0.1554 g stannous octoate catalyst to start heating to 120°C, and after heating, slowly introduce 660 g ethylene oxide monomer into the reactor within 10 h, and control the reaction pressure at 0.3 MPa.

[0069] (4) After the reaction is completed, open the vacuum pump at this temperature for vacuum devolatilization for 2 h, and finally cool and discharge to obtain the acetylenic diol surfactant, and the GPC number average molecular weight is shown in Table 1.

[0070] Example 9

[0071] (1) Put 170 g 3, 6-dimethyl-4-octyne-3, 6-diol and 1140 g caprolactone monomer into the reactor, and replace with nitrogen three times and as a protective gas.

[0072] (2) Increase the temperature to 60°C, and open the vacuum pump for dehydration for 1 h.

[0073] (3) After dehydration, break the vacuum with nitrogen, then add 0.1576 g stannous octoate catalyst to start heating to 150°C, and after heating, slowly introduce 660 g ethylene oxide monomer into the reactor within 5 h, and control the reaction pressure at 0.5 MPa.

[0074] (4) After the reaction is completed, vacuum devolatilization is carried out at this temperature for 1.5 h, and finally the product is obtained by cooling and discharging. The GPC number average molecular weight is shown in Table 1.

[0075] Example 10

[0076] (1) 226 g of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 1140 g of caprolactone monomer are added into a reaction kettle, nitrogen is introduced, and the nitrogen is replaced three times and used as a protective gas.

[0077] (2) The temperature is raised to 60°C, and vacuum dehydration is carried out for 1 h.

[0078] (3) After the dehydration is completed, the vacuum is broken by nitrogen, then 0.162 g of dibutyl tin dilaurate catalyst is added, and the temperature is raised to 160°C. After the temperature is raised, 660 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 4 h, and the pressure of the reaction is controlled to be 0.8 MPa.

[0079] (4) After the reaction is completed, vacuum devolatilization is carried out at this temperature for 1 h, and finally the product is obtained by cooling and discharging. The GPC number average molecular weight is shown in Table 1.

[0080] Example 11

[0081] (1) 254 g of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol and 1140 g of caprolactone monomer are added into a reaction kettle, nitrogen is introduced, and the nitrogen is replaced three times and used as a protective gas.

[0082] (2) The temperature is raised to 60°C, and vacuum dehydration is carried out for 1 h.

[0083] (3) After the dehydration is completed, the vacuum is broken by nitrogen, then 0.164 g of dibutyl tin dilaurate catalyst is added, and the temperature is raised to 130°C. After the temperature is raised, 660 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 9 h, and the pressure of the reaction is controlled to be 1.2 MPa.

[0084] (4) After the reaction is completed, vacuum devolatilization is carried out at this temperature for 2 h, and finally the product is obtained by cooling and discharging. The GPC number average molecular weight is shown in Table 1.

[0085] Comparative Example 1

[0086] (1) 86 g of 2-butyne-1,4-diol and 1140 g of caprolactone monomer are added into a reaction kettle, nitrogen is introduced, and the nitrogen is replaced three times and used as a protective gas.

[0087] (2) The temperature is raised to 60°C, and vacuum dehydration is carried out for 1 h.

[0088] (3) After the dehydration is completed, the vacuum is broken with nitrogen, then 0.221 g of tetrabutyl titanate catalyst is added to start warming to 140℃, after the warming is completed, 1540 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 8 h, and the pressure of the reaction is controlled at 0.6 Mpa.

[0089] (4) After the reaction is completed, the vacuum pump is opened at the temperature to perform vacuum devolatilization for 1.5 h, and finally the product is cooled and discharged to prepare the acetylenic diol surfactant, and the number average molecular weight of GPC is shown in Table 1.

[0090] Comparative Example 2

[0091] (1) 86 g of 2-butyne-1,4-diol and 2850 g of caprolactone monomer are added to the reaction kettle, nitrogen is introduced, and nitrogen is replaced three times and used as a protective gas.

[0092] (2) The temperature is raised to 60℃, and the vacuum pump is opened to perform dehydration for 1 h.

[0093] (3) After the dehydration is completed, the vacuum is broken with nitrogen, then 0.270 g of tetrabutyl titanate catalyst is added to start warming to 140℃, after the warming is completed, 440 g of ethylene oxide monomer is slowly introduced into the reaction kettle within 8 h, and the pressure of the reaction is controlled at 0.6 Mpa.

[0094] (5) After the reaction is completed, the vacuum pump is opened at the temperature to perform vacuum devolatilization for 1.5 h, and finally the product is cooled and discharged to prepare the acetylenic diol surfactant, and the number average molecular weight of GPC is shown in Table 1.

[0095] The acetylenic diol polyether surfactants prepared in the above examples and comparative examples are taken as test objects respectively, and the static surface tension and cloud point temperature thereof are tested.

[0096] The static surface tension of the surfactants prepared in the above examples and comparative examples is tested according to the method of the pull-up liquid film method in GB / T 42415-2023 "Determination of Static Surface Tension of Surfactants".

[0097] The cloud point of the surfactants prepared in the above examples and comparative examples is tested according to the following method.

[0098] Test method: 1 g of sample was weighed to 0.01 g, and was placed in an iodine flask, 100 mL of distilled water was added, and the sample was shaken to dissolve completely. The sample solution was taken with a pipette and was added to an ampoule to a depth of about 40 mm, the ampoule was sealed with fire, and was covered with a wire mesh, and was moved into a beaker containing a heat conductor, with the upper end of the ampoule extending slightly out of the beaker. To prevent ampoule explosion due to poor sealing, a safety glass or transparent plastic protective screen was placed in front of the device, a thermometer was inserted into the heating bath beside the ampoule, a magnetic stirrer was started, and heating was performed. When the liquid in the ampoule became turbid, heating was stopped, and stirring was continued until the turbidity disappeared completely, and the temperature was recorded. The difference between two parallel measurements was not more than 0.5°C

[0099] Table 1 product data of each example

[0100]

[0101]

[0102] As can be seen from Examples 1-4 and Comparative Example 2, the more the hydrophobic groups (PCL segments) in the surfactant molecules, the higher the cloud point will be. It is speculated that because the hydrophobic groups increase the intermolecular attraction, causing intermolecular aggregation, micelles are formed, and the formation of micelles is the main reason for the appearance of the cloud point. With the increase of the caprolactone segment, the hydrophobicity of the surfactant is enhanced, the water solubility is reduced, and the number of hydrogen bonds formed with water is reduced, so the cloud point is also reduced.

[0103] As can be seen from Example 2, Examples 5-7, and Comparative Example 2, with the increase of the number of hydrophilic groups, the cloud point of the surfactant will first increase, and then the number of hydrophilic groups will increase to a certain extent, and the cloud point will not change much. Moreover, if the number of hydrophilic groups is too large, as can be seen from Comparative Example 1, the surface tension will increase significantly.

[0104] As can be seen from Examples 1-4 and Comparative Example 2, with the increase of the number of polycaprolactone segments, the surface tension first decreases and then increases. As can be seen from Example 2, Examples 5-7, and Comparative Example 2, with the increase of the number of PEO segments, the surface tension also first decreases and then increases. This indicates that it is not the more polycaprolactone segments or the fewer PEO segments that make the surface tension smaller, but rather the two segments need to work together to prepare a surfactant with very low surface tension.

[0105] Although the embodiments of the present application have been disclosed as above, they are not limited to the use listed in the specification and the embodiments, and can be fully applied to various fields suitable for the present application, and additional modifications can be easily realized by those skilled in the art, and therefore the present application is not limited to the specific details and shown herein without departing from the general concept defined by the claims and the equivalent scope.

Claims

1. An acetylenic diol compound, characterized by, The chemical structural formula of the acetylene diol compound is as follows: ； Wherein, R1, R2, R3 and R4 are H or alkyl; Both n and p are the number of oxirane, and the value range of n+p is 10-25; Both m and q are the number of caprolactone, and the value range of m+q is 5-20.

2. A method for producing an acetylenic diol compound, characterized by, The method comprises the following steps: Step one, acetylene diol monomer and caprolactone monomer are added into a reaction kettle, and nitrogen is introduced as a protective gas; Step two, the temperature of the reaction kettle is increased to 40-60℃, and a vacuum pump is opened for dehydration; Step three, after dehydration, a catalyst is added to start heating to the reaction temperature, and after heating is completed, the acetylene diol monomer is slowly introduced into the reaction kettle, and the pressure of the reaction is controlled; Step four, after the reaction is completed, the vacuum pump is opened for vacuum devolatilization for 1-2h, and finally the product is cooled and discharged to obtain the acetylene diol compound of claim 1.

3. The method for preparing acetylenic diol compounds as described in claim 2, characterized in that, In the step one, the acetylene diol monomer is one of 2-butyne-1,4-diol, 2,5-dimethylhexyne diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol.

4. The method for preparing acetylenic diol compounds as described in claim 3, characterized in that, The acetylene diol monomer is 2-butyne-1,4-diol.

5. The method for preparing acetylenic diol compounds as described in claim 2, characterized in that, In the step one, the mass ratio of the acetylene diol monomer and the caprolactone monomer is 86-254:570-2280.

6. The method for preparing acetylenic diol compounds according to claim 2, characterized in that, The catalyst is one or more of stannous octoate, stannous isooctoate, dibutyltin dilaurate, and tetrabutyl titanate; the mass ratio of the acetylene diol monomer and the catalyst is 86-254:0.08768-0.22448.

7. The method for preparing acetylenic diol compounds according to claim 2, characterized in that, The mass ratio of the acetylene diol monomer and the oxirane monomer is 86-254:440-1100.

8. The method for preparing acetylenic diol compounds as described in claim 2, characterized in that, In the step three, the reaction temperature is 120℃-160℃, and the reaction pressure is 0.2-1.2Mpa.

9. Use of the acetylenic diol compound according to claim 1, characterized in that, The acetylene diol compound is used as a surfactant.

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