Acetylene glycol compound as well as preparation method and application thereof

Abstract

The invention discloses an alkynediol compound as well as a preparation method and application thereof, and the preparation method comprises the following steps: step 1, adding an alkynediol monomer and a caprolactone monomer into a reaction kettle, and introducing nitrogen as shielding gas; 2, raising the temperature of the reaction kettle to 40-60 DEG C, and starting a vacuum pump for dehydration; step 3, after dehydration is completed, adding a catalyst, starting to heat to a reaction temperature, slowly introducing an ethylene oxide monomer into the reaction kettle after heating is completed, and controlling the reaction pressure; and step 4, after the reaction is finished, opening a vacuum pump to carry out vacuum devolatilization for 1-2 hours, and finally cooling and discharging to obtain the alkyne diol compound. Therefore, the surfactant provided by the invention has better high temperature resistance and acid and alkali resistance than common alkyne diol polyether surfactants, and has a wider application range; the environment-friendly water-based paint is nontoxic, can be degraded, can be quickly degraded even if being discharged into the environment, is very environment-friendly and has relatively low surface tension.

Description

Technical Field

[0001] The present invention belongs to the field of chemistry, and in particular relates to acetylene glycol compounds, a preparation method and an application thereof. Background Art

[0002] Surfactants are substances that significantly reduce the surface tension of a target solution. They possess fixed hydrophilic and lipophilic groups that can be arranged in a directional pattern on the surface of the solution. Surfactants have a range of physical and chemical effects, including wetting or anti-sticking, emulsification or demulsification, foaming or defoaming, solubilization, dispersion, cleaning, corrosion protection, and antistatic properties.

[0003] There are many types of surfactants with different functions and applications. Alkynol surfactants, also known as acetylene glycol surfactants, have strong polarity and hydrophilicity due to the -C≡C- and -OH groups in the acetylene glycol molecule, while the hydrocarbon group brings hydrophobicity, which makes acetylene glycol an excellent nonionic surfactant.

[0004] However, the vast majority of acetylenic diol compounds on the market are acetylenic diol polyether surfactants, formed by copolymerizing acetylenic diol with ethylene oxide or propylene oxide. These surfactants, due to their high ether bond content, are not heat-resistant and are susceptible to inactivation or reduced surface activity in high-temperature applications such as plastic cleaning, industrial cleaning, and oil extraction. Furthermore, these surfactants have a low cloud point and precipitate or partially precipitate at higher temperatures, thus affecting their surface activity. While acetylenic diol fluorinated polyether surfactants offer strong chemical and thermal stability and outstanding high-temperature resistance, they are difficult to degrade and toxic when released into the environment, posing a significant health risk. While non-toxic, silane-containing acetylenic diol compounds are costly and expensive, and their ability to reduce surface tension lacks a significant advantage over other silicone surfactants.

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

[0006] In order to solve the above problems, the present invention discloses an acetylene glycol compound, a preparation method and application thereof.

[0007] To achieve the above object, the technical solution of the present invention is:

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

[0009]

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

[0011] Both n and p are the number of ethylene oxides, and the value of n+p ranges from 10 to 25;

[0012] Both m and q are the number of caprolactones, and the value of m+q ranges from 5 to 20.

[0013] A method for preparing an acetylene glycol compound comprises the following steps:

[0014] Step 1: adding acetylene glycol monomer and caprolactone monomer into a reaction kettle, and introducing nitrogen as a protective gas;

[0015] Step 2: Raise the temperature of the reactor to 40-60°C and turn on the vacuum pump for dehydration;

[0016] Step 3: After dehydration is completed, add the catalyst and start heating to the reaction temperature. After heating is completed, slowly introduce ethylene oxide monomer into the reactor to control the reaction pressure;

[0017] Step 4: After the reaction is completed, turn on the vacuum pump to carry out vacuum devolatilization for 1-2 hours, and finally cool the material to obtain the acetylene glycol compound according to claim 1.

[0018] Further improvement, in step 1, the acetylene diol monomer is one of 2-butyne-1,4-diol, 2,5-dimethylhexynediol, 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.

[0019] In a further improvement, the acetylene diol monomer is 2-butyne-1,4-diol.

[0020] As a further improvement, in step 1, the mass ratio of the acetylene glycol monomer to the caprolactone monomer is 86-254:570-2280.

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

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

[0023] As a further improvement, in step three, the reaction temperature is 120°C-160°C, preferably 140°C, and the reaction pressure is 0.2-1.2 MPa, preferably 0.6 MPa.

[0024] A use of an acetylene glycol compound, wherein the acetylene glycol compound is as described above and is used as a surfactant.

[0025] Advantages of the present invention:

[0026] 1. Generally speaking, the cloud point of a surfactant decreases as the number of hydrophobic segments increases. However, the present invention adopts a PCL segment as the hydrophobic segment structure of the surfactant. Since the PCL segment contains an ester bond, which is a polar structure, the structural part containing the ester bond can form hydrogen bonds with water in water. Moreover, the PCL segment and the PEO segment are also linear structures without steric hindrance, and thus are more likely to form hydrogen bonds with water in water. Within a certain range of water solubility, the interaction between the two will increase the cloud point of the surfactant of the present invention, thereby increasing the temperature range of use of the surfactant. In addition, the heat resistance and acid and alkali resistance of the ester group are superior to those of the ether group. Therefore, the surfactant of the present invention has better high temperature resistance and acid and alkali resistance than general acetylene glycol polyether surfactants, and has a wider range of applications.

[0027] 2. The polycaprolactone segment and polyethylene oxide segment in the present invention are also biodegradable, so the surfactant of the present invention is non-toxic and degradable, and can be rapidly degraded even if discharged into the environment, which is very environmentally friendly.

[0028] 3. In the present invention, the PCL segment is a hydrophobic segment and the PEO segment is a hydrophilic segment, and the two segments jointly adjust the hydrophilic-lipophilic balance value of the surfactant. Since the PCL segment and the PEO segment are linear structures, this structure is conducive to the formation of a tight monolayer at the interface, reducing the molecular gap, thereby facilitating the formation of micelles and close arrangement of the interface. The synthesized surfactant has low surface tension and good surface activity. DETAILED DESCRIPTION

[0029] The present invention is further described below with reference to the examples.

[0030] Example 1

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

[0032] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

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

[0034] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol 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 were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0037] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0038] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.133 g of tetrabutyl titanate catalyst was added and the temperature was raised to 140° C. After the temperature was raised, 440 g of ethylene oxide monomer was slowly introduced into the reactor within 5 h, and the reaction pressure was controlled at 0.6 MPa.

[0039] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol 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 were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0042] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0043] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.178 g of tetrabutyl titanate catalyst was added and the temperature was raised to 140° C. After the temperature was raised, 440 g of ethylene oxide monomer was slowly introduced into the reactor within 6 h, and the reaction pressure was controlled at 0.6 MPa.

[0044] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol 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 were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0047] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0048] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.225 g of tetrabutyl titanate catalyst was added and the temperature was raised to 140° C. After the temperature was raised, 440 g of ethylene oxide monomer was slowly introduced into the reactor within 7 h, and the reaction pressure was controlled at 0.6 MPa.

[0049] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. The GPC number average molecular weight is shown in Table 1.

[0050] Example 5

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

[0052] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0053] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.15 g of tetrabutyl titanate catalyst was added and the temperature was raised to 140°C. After the temperature was raised, 660 g of ethylene oxide monomer was slowly introduced into the reactor within 6 hours, and the reaction pressure was controlled at 0.6 MPa.

[0054] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. The GPC number average molecular weight is shown in Table 1.

[0055] Example 6

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

[0057] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0058] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.168 g of tetrabutyl titanate catalyst was added and the temperature was raised to 140°C. After the temperature was raised, 880 g of ethylene oxide monomer was slowly introduced into the reactor within 7 hours, and the reaction pressure was controlled at 0.6 MPa.

[0059] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. The GPC number average molecular weight is shown in Table 1.

[0060] Example 7

[0061] (1) 86 g of 2-butyne-1,4-diol and 1140 g of caprolactone monomer were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0062] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0063] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.186 g of tetrabutyl titanate catalyst was added and the temperature was raised to 140°C. After the temperature was raised, 1100 g of ethylene oxide monomer was slowly introduced into the reactor within 7 hours, and the reaction pressure was controlled at 0.6 MPa.

[0064] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. The GPC number average molecular weight is shown in Table 1.

[0065] Example 8

[0066] (1) 142 g of 2,5-dimethylhexynediol and 1140 g of caprolactone monomer were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0067] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0068] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.1554 g of stannous octoate catalyst was added and the temperature was raised to 120° C. After the temperature was raised, 660 g of ethylene oxide monomer was slowly introduced into the reactor within 10 h, and the reaction pressure was controlled at 0.3 MPa.

[0069] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 2 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. The GPC number average molecular weight is shown in Table 1.

[0070] Example 9

[0071] (1) 170 g of 3,6-dimethyl-4-octyne-3,6-diol and 1140 g of caprolactone monomer were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0072] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0073] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.1576 g of stannous octoate catalyst was added and the temperature was raised to 150° C. After the temperature was raised, 660 g of ethylene oxide monomer was slowly introduced into the reactor within 5 h, and the reaction pressure was controlled at 0.5 MPa.

[0074] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. 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 were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0077] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0078] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.162 g of dibutyltin dilaurate catalyst was added and the temperature was raised to 160°C. After the temperature was raised, 660 g of ethylene oxide monomer was slowly introduced into the reactor within 4 h, and the reaction pressure was controlled at 0.8 MPa.

[0079] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1 hour, and the material is finally cooled to obtain an acetylene glycol surfactant. 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-dodecene-5,8-diol and 1140 g of caprolactone monomer were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0082] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0083] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.164 g of dibutyltin dilaurate catalyst was added and the temperature was raised to 130° C. After the temperature was raised, 660 g of ethylene oxide monomer was slowly introduced into the reactor within 9 hours, and the reaction pressure was controlled at 1.2 MPa.

[0084] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 2 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. 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 were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0087] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0088] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.221 g of tetrabutyl titanate catalyst was added and the temperature was raised to 140°C. After the temperature was raised, 1540 g of ethylene oxide monomer was slowly introduced into the reactor within 8 hours, and the reaction pressure was controlled at 0.6 MPa.

[0089] (4) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. The GPC number average molecular weight 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 were added to a reaction kettle, and nitrogen was introduced. The nitrogen was replaced three times and used as a protective gas.

[0092] (2) Raise the temperature to 60°C and turn on the vacuum pump to dehydrate for 1 hour.

[0093] (3) After dehydration, the vacuum was broken with nitrogen, and then 0.270 g of tetrabutyl titanate catalyst was added and the temperature was raised to 140° C. After the temperature was raised, 440 g of ethylene oxide monomer was slowly introduced into the reactor within 8 h, and the reaction pressure was controlled at 0.6 MPa.

[0094] (5) After the reaction is completed, the vacuum pump is turned on at the same temperature to carry out vacuum devolatilization for 1.5 hours, and the material is finally cooled to obtain an acetylene glycol surfactant. The GPC number average molecular weight is shown in Table 1.

[0095] The acetylene glycol polyether surfactants prepared in the above examples and comparative examples were respectively taken as test objects to test their static surface tension and cloud point temperature.

[0096] The static surface tension of the surfactants prepared in the above examples and comparative examples was tested according to the liquid film pulling method in GB / T 42415-2023 “Determination of static surface tension of surfactants”.

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

[0098] Test method: Weigh 1g of the sample, accurate to 0.01g, place the sample in an iodine volumetric flask, add 100mL of distilled water, shake well, and dissolve the sample completely. Use a pipette to draw the sample solution into the ampoule to a depth of about 40mm, seal the mouth of the ampoule with fire, cover the ampoule with a wire mesh, and move it into a beaker equipped with a heat conductor, with the upper end of the ampoule slightly extending out of the beaker. In order to prevent the ampoule from bursting due to poor sealing, a safety glass or transparent plastic protective screen should be placed in front of the device, insert the thermometer next to the ampoule in the heating bath, start the magnetic stirrer and heat. When the liquid in the ampoule becomes turbid, stop heating, continue stirring, let it cool, and record the temperature when the turbidity completely disappears. Perform two parallel measurements, and the difference between the parallel measurement results should not exceed 0.5℃

[0099] Table 1 Product data of each embodiment

[0100]

[0101]

[0102] As can be seen from Examples 1-4 and Comparative Example 2, the cloud point increases with increasing hydrophobic groups (PCL segments) in the surfactant molecule. This is presumably because hydrophobic groups enhance intermolecular attraction, leading to intermolecular aggregation and the formation of micelles. The formation of micelles is the primary cause of the cloud point. As the number of caprolactone segments increases, the surfactant becomes more hydrophobic, its water solubility decreases, and the number of hydrogen bonds formed with water decreases, resulting in a lower cloud point.

[0103] As can be seen from Example 2, Examples 5-7, and Comparative Example 2, as the number of hydrophilic groups increases, the cloud point of the surfactant initially rises. However, once the number of hydrophilic groups reaches a certain level, the cloud point remains essentially unchanged. Furthermore, as can be seen from Comparative Example 1, if there are too many hydrophilic groups, the surface tension increases significantly.

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

[0105] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the description and the embodiments. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and shown here.

Claims

1. An acetylene glycol compound, characterized in that The chemical structural formula of the acetylene glycol compound is as follows: Wherein, R1, R2, R3 and R4 are H or alkyl Both n and p are the number of ethylene oxides, and the value of n+p ranges from 10 to 25; Both m and q are the number of caprolactones, and the value of m+q ranges from 5 to 20.

2. A method for preparing an acetylene glycol compound, characterized in that: The steps include: Step 1: adding acetylene glycol monomer and caprolactone monomer into a reaction kettle, and introducing nitrogen as a protective gas; Step 2: Raise the temperature of the reactor to 40-60°C and turn on the vacuum pump for dehydration; Step 3: After dehydration is completed, add the catalyst and start heating to the reaction temperature. After heating is completed, slowly introduce ethylene oxide monomer into the reactor to control the reaction pressure; Step 4: After the reaction is completed, turn on the vacuum pump to carry out vacuum devolatilization for 1-2 hours, and finally cool the material to obtain the acetylene glycol compound according to claim 1.

3. The method for preparing an acetylene glycol compound according to claim 2, wherein In the step 1, the acetylene diol monomer is one of 2-butyne-1,4-diol, 2,5-dimethylhexynediol, 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 an acetylene glycol compound according to claim 3, wherein The acetylene diol monomer is 2-butyne-1,4-diol.

5. The method for preparing an acetylene glycol compound according to claim 2, wherein In the step 1, the mass ratio of the acetylene glycol monomer to the caprolactone monomer is 86-254:570-2280.

6. The method for preparing an acetylene glycol compound according to claim 2, wherein The catalyst is one or more of stannous octoate, stannous isooctanoate, dibutyltin dilaurate, and tetrabutyl titanate, preferably tetrabutyl titanate. The mass ratio of the acetylene glycol monomer to the catalyst is 86-254:0.08768-0.22448.

7. The method for preparing an acetylene glycol compound according to claim 2, wherein The mass ratio of the acetylene glycol monomer to the ethylene oxide monomer is 86-254:440-1100.

8. The method for preparing an acetylene glycol compound according to claim 2, wherein In the step 3, the reaction temperature is 120° C.-160° C., preferably 140° C., and the reaction pressure is 0.2-1.2 MPa, preferably 0.6 MPa.

9. A use of an acetylene glycol compound, characterized in that: The acetylene glycol compound is as described in any one of claims 1 to 9, and the acetylene glycol compound is used as a surfactant.

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