Solvent-free preparation process of epoxy polyether modified silicone oil

Abstract

The invention relates to a method for preparing epoxy polyether modified silicone oil without using a solvent, which comprises the following steps: modifying hydrogen-containing silicone oil by using allyl polyether to prepare polyether modified silicone oil, and then reacting with epoxy polyether to prepare the epoxy polyether modified silicone oil. According to the method, no solvent is used in the reaction process, the safety of the product at a downstream application end can be guaranteed, meanwhile, the epoxy group side reaction caused by the solvent is avoided, and the efficient, safe and environment-friendly effects are achieved.

Description

Technical Field

[0001] The invention relates to a solvent-free preparation process of epoxy polyether modified silicone oil, belonging to the technical field of chemical industry. Background Art

[0002] Epoxy polyether silicone oil is the raw material of a new structure of silicone softening finishing agent that has developed most rapidly in the past decade. Compared with traditional silicone oil, the linearity of polyether amino block copolymer silicone oil produced by epoxy polyether silicone oil is more obvious, and it has self-emulsification, which can self-emulsify in water to form a stable emulsion, and the softening finishing effect is also more prominent (especially on chemical fiber flannel). At present, the epoxy polyether silicone oil used in the market is prepared and produced using isopropyl alcohol or ethylene glycol monobutyl ether as solvent.

[0003] With the improvement of environmental protection requirements and factory processing requirements for odor, many companies also use solvents with less odor such as propylene glycol butyl ether or propylene glycol butyl ether to replace the above solvents to obtain odorless and environmentally friendly block copolymer silicone oils. However, the use of solvents leads to a decrease in the feel during finishing. Moreover, the solvent itself does not have a finishing effect, and it remains in the system after emulsification, which has a certain carcinogenicity to the human body. At the same time, due to the presence of solvents, the epoxy groups of epoxy polyether silicone oils are isomerized, reducing the use effect. However, the two raw materials (hydrogen-containing silicone oil and epoxy polyether) used to prepare epoxy polyether silicone oils are incompatible and are difficult to react under solvent-free conditions.

[0004] Patent CN109354690B discloses a solvent-free method for preparing epoxy-terminated polyether-modified silicone oil, which uses low-hydrogen silicone oil and allyl epoxy-terminated polyether as raw materials, activated iron phosphate as phase transfer catalyst, and a corresponding preparation process, using phase transfer catalyst instead of solvent to synthesize epoxy-terminated polyether-modified silicone oil. The iron phosphate catalyst used in the method will reduce the reaction activity of the platinum catalyst on the one hand, and the introduction of iron ions will cause the product to turn yellow, resulting in difficulties in downstream applications. Summary of the invention

[0005] The present invention provides a method for preparing epoxy polyether modified silicone oil without using a solvent, wherein before the hydrogen-containing silicone oil reacts with the epoxy polyether, an appropriate amount of allyl polyether is added to the hydrogen-containing silicone oil for reaction, and then the epoxy polyether is added to the obtained reaction mixture for reaction. The method does not use any substance as a solvent.

[0006] According to the present invention, the method for preparing epoxy polyether modified silicone oil without using a solvent comprises the following steps:

[0007] 1) The hydrogen-containing silicone oil represented by Formula 1 and the allyl polyether represented by Formula 2 react under the action of a catalyst to obtain a reaction product mixture;

[0008]

[0009] in:

[0010] In formula 1:

[0011] Each R, R1, and R2 are independently C1-C 10 Alkyl, C3-C 10 The cycloalkyl or phenyl group is preferably a C1-C6 alkyl group, a C3-C6 cycloalkyl or phenyl group; the alkyl group is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl; the cycloalkyl group is, for example, cyclohexyl; more preferably, methyl or phenyl;

[0012] Each R3 is independently a C1-C3 alkyl group or hydrogen; preferably the alkyl group is methyl;

[0013] m1 and m2 are each independently an integer of 0-300 and are not both 0; preferably, each independently an integer of 0-120, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 , 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 72, 75, 80, 85, 90, 95, 100, 110, 115, etc.;

[0014] In formula 2:

[0015] R4 is C1-C 20 An alkylene group is preferably a C1-C5 alkylene group, such as a methylene group, a C2 alkylene group, a C3 alkylene group, a C4 alkylene group, etc., and more preferably a methylene group;

[0016] n1, n2, n3 are the same or different, and are each independently an integer of 0-200, and are not 0 at the same time; preferably an integer of 0-100, more preferably an integer of 0-70, for example 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, etc.;

[0017] 2) Adding the terminal epoxy polyether shown in formula 3 to the reaction product mixture obtained in step 1) to react to obtain epoxy polyether-modified silicone oil:

[0018]

[0019] Among them, in formula 3:

[0020] R5 is C1-C 20 An alkylene group is preferably a C1-C5 alkylene group, such as a methylene group, a C2 alkylene group, a C3 alkylene group, a C4 alkylene group, etc., and more preferably a methylene group;

[0021] R6 is (CH2) n7 O(CH2) n8 ;

[0022] n4, n5, n6, n7, n8 are the same or different, and are each independently an integer of 0-200, and are not all 0; preferably an integer of 0-100, more preferably an integer of 0-70, for example 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, etc.

[0023] According to the present invention, taking the molar amount of Si-H in the hydrogenated silicone oil shown in Formula 1 as 1, the total molar amount of CH2=CH of the allyl polyether shown in Formula 2 and the allyl epoxy polyether shown in Formula 3 is 0.9-1.6 times the molar amount of Si-H in the hydrogenated silicone oil shown in Formula 1; preferably, the total molar amount of CH2=CH is 1.05-1.4 times the molar amount of Si-H.

[0024] The molar amount of CH2=CH in the allyl polyether shown in Formula 2 accounts for 1-15% of the total molar amount of CH2=CH; the molar amount of CH2=CH in the allyl-terminated epoxy polyether shown in Formula 3 accounts for 85-99% of the total molar amount of CH2=CH. Preferably, the molar amount of CH2=CH in the allyl polyether shown in Formula 2 accounts for 5-15% of the total molar amount of CH2=CH; the molar amount of CH2=CH in the allyl-terminated epoxy polyether shown in Formula 3 accounts for 85-95% of the total molar amount of CH2=CH.

[0025] According to the present invention, the catalyst in step 1) is a platinum-containing compound catalyst; preferably, the platinum-containing compound catalyst is at least one of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex, tetramethyltetravinylcyclotetrasiloxane platinum complex and chloroplatinic acid.

[0026] Based on the total mass of the reactants of formula 1, formula 2 and formula 3 in steps 1) and 2), the amount of the platinum-containing compound catalyst is 1-20 ppm; preferably, based on the total mass of the reactants, the amount of the platinum-containing compound catalyst is 5-10 ppm.

[0027] According to the present invention, the reaction temperature of step 1) is 60-100° C., and the reaction time is 0.2-10 h; preferably, the reaction temperature is 70-90° C., and the reaction time is 0.4-4 h.

[0028] The reaction temperature of step 2) is 60-100°C and the reaction time is 1-20h; preferably, the reaction temperature is 70-90°C and the reaction time is 1.5-6h.

[0029] The inventors of the present invention have found that by using an appropriate amount of allyl polyether to react with hydrogen-containing silicone oil first, the hydrophobicity of the hydrogen-containing silicone oil can be reduced, and the HLB value (hydrophilic-lipophilic balance value) of the obtained reaction product mixture can be increased. When the terminal epoxy polyether is added, the compatibility of the hydrogen-containing silicone oil and the terminal epoxy polyether can be improved, so that the two raw materials can be fully contacted to react and obtain the final product-epoxy polyether modified silicone oil. Since no substance as a solvent is used in the entire reaction, the obtained final product does not contain any solvent, which can ensure the safety of the product at the downstream application end, while avoiding the epoxy side reaction caused by the solvent, and achieving the effect of high efficiency, safety and environmental protection.

[0030] Without being limited to a specific reaction mechanism, in the reaction of step 1), the olefinic bond of the allyl polyether undergoes a silylation reaction with the SiH group of the hydrogenated silicone oil to obtain an allyl polyether-modified hydrogenated silicone oil, wherein the allyl polyether-modified hydrogenated silicone oil serves to increase the HLB value of the reaction product mixture, and the compatibility of the epoxy-terminated polyether added thereto with the reaction product mixture is improved, thereby improving the compatibility of the hydrogenated silicone oil with the epoxy-terminated polyether, so that the two raw materials can fully contact and react. DETAILED DESCRIPTION

[0031] The technical solution of the present invention is further described in detail below through specific embodiments. It should be understood that the implementation of the present invention is not limited to the following embodiments, and any form of modification and / or change made to the present invention will fall within the protection scope of the present invention.

[0032] In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used can be purchased from the market or are commonly used in the art. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0033] In the following examples, the molecular formula of allyl epoxy polyether is POxy ” represents an epoxy group.

[0034] Example 1

[0035] The solvent-free preparation method of epoxy polyether silicone oil has the following specific steps:

[0036] (1) 300 g of end-hydrogenated silicone oil H Si(CH3)2O 1 / 2 [Si(CH3)2O] 106 O 1 / 2 Si(CH3)2H (H content 0.025%) and 3g of allyl polyether (CH2=CHCH2O(EO)9H) were mixed evenly, and 8ppm of Pt catalyst was added under stirring. The temperature was raised to 75°C, and the reaction was kept warm for 30 minutes to test the turbidity point of the product.

[0037] (2) Add 30 g of allyl-terminated epoxy polyether (CH2=CHCH2O(EO)7CH2CH2CH2OCH2E POxy ), keep warm for 2h, test the residual H and residual vinyl in the reactant, recorded as S1.

[0038] Comparative Example 1

[0039] 300g of hydrogen-terminated silicone oil H Si(CH3)2O 1 / 2 [Si(CH3)2O] 106 O 1 / 2Si(CH3)2H (H content 0.025%) and 34g allyl-terminated epoxy polyether (CH2=CHCH2O(EO)7CH2CH2CH2OCH2E POxy ) were mixed evenly, 8 ppm Pt catalyst was added under stirring, the temperature was raised to 75°C, and the reaction was kept at this temperature for 3 hours. The cloud point of hydrogenated silicone oil was tested, and the residual H and residual vinyl in the reactants were tested, which was recorded as B1.

[0040] Comparative Example 4

[0041] 300g of hydrogen-terminated silicone oil H Si(CH3)2O 1 / 2 [Si(CH3)2O] 106 O 1 / 2 Si(CH3)2H (H content 0.025%), 100g solvent IPA and 34g allyl-terminated epoxy polyether (CH2=CHCH2O(EO)7CH2CH2CH2OCH2E POxy ) were mixed evenly, 8ppm Pt catalyst was added under stirring, the temperature was raised to 75°C, the reaction was kept at this temperature for 3h, and then the temperature was raised to 100°C, and the reaction was carried out under negative pressure at -0.098MPa (absolute pressure) for 2h. The cloud point of hydrogenated silicone oil was tested, and the residual H and residual vinyl in the reactants were tested, which was recorded as B1'.

[0042] Example 2

[0043] The solvent-free preparation method of epoxy polyether silicone oil comprises the following specific steps:

[0044] (1) 313 g of hydrogenated silicone oil (CH3)3SiO 1 / 2 [Si(CH3)2O] 68 [HSi(CH3)O]6O 1 / 2 Si(CH3)3 (H content 0.1%) was mixed evenly with 18.7g of allyl polyether (CH2=CHCH2O(PO)4(EO)4H), and 8ppm of Pt catalyst was added under stirring. The temperature was raised to 75°C, and the reaction was kept warm for 30 minutes. The turbidity point of the product was tested.

[0045] (2) Add 168.3 g of allyl-terminated epoxy polyether (CH2=CHCH2O(PO)4(EO)4CH2CH2CH2OCH2E POxy ), and continue to keep warm for 2h, recorded as S2.

[0046] Comparative Example 2

[0047] 313 g of hydrogenated silicone oil (CH3)3SiO 1 / 2 [Si(CH3)2O] 68 [HSi(CH3)O]6O 1 / 2Si(CH3)3 (H content 0.1%) and 178g allyl-terminated epoxy polyether (CH2=CHCH2O(PO)4(EO)CH2CH2CH2OCH2E POxy ) were mixed evenly, 8 ppm Pt catalyst was added under stirring, the temperature was raised to 75°C, and the reaction was kept at this temperature for 3 hours. The cloud point of hydrogenated silicone oil was tested, and the residual H and residual vinyl in the reactants were tested, which was recorded as B2.

[0048] Comparative Example 5

[0049] 313 g of hydrogenated silicone oil (CH3)3SiO 1 / 2 [Si(CH3)2O] 68 [HSi(CH3)O]6O 1 / 2 Si(CH3)3 (H content 0.1%), 100g solvent IPA and 178g allyl-terminated epoxy polyether (CH2=CHCH2O(PO)4(EO)4CH2CH2CH2OCH2E POxy ) were mixed evenly, 8ppm Pt catalyst was added under stirring, the temperature was raised to 75°C, the reaction was kept at this temperature for 3h, and then the temperature was raised to 100°C, and the reaction was carried out under negative pressure at -0.098MPa for 2h. The cloud point of hydrogenated silicone oil was tested, and the residual H and residual vinyl in the reactants were tested, which was recorded as B2'.

[0050] Example 3

[0051] The solvent-free preparation method of epoxy polyether silicone oil comprises the following specific steps:

[0052] (1) 130 g of side-end hydrogenated silicone oil H Si(CH 3 ) 2 O 1 / 2 [Si(CH3)2O] 72 [HSi(CH3)O]6O 1 / 2 Si(CH3)2H (H content 0.1%) and 15g allyl polyether (CH2=CHCH2O(PO) 21 H) Mix well, add 8 ppm Pt catalyst under stirring, raise the temperature to 75° C., keep the temperature for 30 min and test the turbidity point of the product.

[0053] (2) Add 170 g of allyl-terminated epoxy polyether (CH2=CHCH2O(PO)) to the product mixture of step (1) 18 CH2CH2CH2OCH2E POxy ), and continue to keep warm for 2h, recorded as S3.

[0054] Comparative Example 3

[0055] 130 g of side-end hydrogenated silicone oil H Si(CH3)2O 1 / 2 [Si(CH3)2O] 72[HSi(CH3)O]6O 1 / 2 Si(CH3)2H (content 0.1%) and 187g allyl-terminated epoxy polyether (CH2=CHCH2O(PO) 18 CH2CH2CH2OCH2E POxy ) were mixed evenly, 8 ppm Pt catalyst was added under stirring, the temperature was raised to 75°C, and the reaction was kept at this temperature for 3 hours. The cloud point of hydrogenated silicone oil was tested, and the residual H and residual vinyl in the reactants were tested, which was recorded as B3.

[0056] Comparative Example 6

[0057] 130 g of side-end hydrogenated silicone oil H Si(CH3)2O 1 / 2 [Si(CH3)2O] 72 [HSi(CH3)O]6O 1 / 2 Si(CH3)2H (H content 0.1%), 100g solvent IPA and 187g allyl-terminated epoxy polyether (CH2=CHCH2O(PO) 18 CH2CH2CH2OCH2E POxy ) were mixed evenly, 8ppm Pt catalyst was added under stirring, the temperature was raised to 75°C, the reaction was kept at this temperature for 3h, and then the temperature was raised to 100°C, and the reaction was carried out under negative pressure at -0.098MPa for 2h. The cloud point of hydrogenated silicone oil was tested, and the residual H and residual vinyl in the reactants were tested, which was recorded as B3'.

[0058] Test Case

[0059] (1) Vinyl content was measured using Agilent GC-8850;

[0060] (2) Molecular weight and molecular weight distribution were tested using Agilent GPC-1260;

[0061] (3) The residual H content was measured using Agilent Cary 630 FTIR.

[0062] (4) Haze test was performed using an X-Rite visible light spectrophotometer (CI7800).

[0063] (5) The HLB value was tested using the turbidity point method. The turbidity point was tested using a 10% aqueous solution. HLB = 0.098X + 4.02, where X is the turbidity point.

[0064] (6) Volatile matter test conditions: 150°C / no air blowing / 2h / 1g, aluminum cup 40×30mm.

[0065] The test results of vinyl and residual hydrogen are shown in Table 1 below:

[0066] Table 1

[0067]

[0068]

[0069] The test results in Table 1 show that after the completion of Examples 1, 2, and 3, there is almost no residual vinyl and Si-H in the system, proving that the vinyl and Si-H have completely reacted. In Comparative Examples 1, 2, and 3, there is almost no reaction between the vinyl and Si-H, and after the completion of Comparative Examples 4, 5, and 6, there is almost no residual vinyl and Si-H in the system, proving that the vinyl and Si-H have completely reacted. The results prove that the residual vinyl and Si-H of the product prepared by the method of the present application can reach the same level as the traditional solvent method, indicating that the epoxy polyether modified silicone oil can be prepared by the method without solvent.

[0070] The test results of haze, cloud point and volatile matter are shown in Table 2 below:

[0071] Table 2

[0072] Serial number Haze Cloud point / ℃ Volatile matter / % S1 0.93 12.5 0.12 B1 79.23 -22 1.53 B1’ 1.12 -22 0.89 S2 1.02 14.3 0.09 B2 87.98 -21 1.43 B2’ 1.21 -22 1.12 S3 1.53 17.3 0.07 B3 88.34 -22 1.84 B3’ 1.77 -22 1.73

[0073] The test results in Table 2 show that the haze of S1, S2, S3, B1', B2', and B3' after the reaction is completed is less than 2Hazn, while the haze of B1, B2, and B3 is greater than 70Hazn, proving that the two raw materials are incompatible without changing the HLB or adding an external solvent; by testing the cloud points of the intermediate products of S1, S2, and S3 and the hydrogenated silicone oils of B1, B2, B3, B1', B2', and B3', it can be seen that adding a polyether segment can increase the hydrophilicity of the hydrogenated silicone oil and reduce its hydrophobicity; by testing the volatile matter of S1, S2, S3, B1, B2, B3, B1', B2', and B3', it can be seen that even if B1', B2', and B3' have been subjected to high-temperature degassing, the solvent remaining in the system after the reaction cannot be completely removed.

[0074] The GPC test results are shown in Table 3 below:

[0075] Table 3

[0076]

[0077] Table 3 shows the molecular weight information of the compounds. It can be seen that only the molecular weight of the raw materials can be tested in B1, B2, and B3, indicating that comparative examples 1-3 cannot undergo hydrosilylation reaction without solvent.

Claims

1. A method for preparing epoxy polyether modified silicone oil without using solvent, characterized in that: The following steps are involved: 1) The hydrogen-containing silicone oil represented by Formula 1 and the allyl polyether represented by Formula 2 react under the action of a catalyst to obtain a reaction product mixture; in: In formula 1: Each R, R1, and R2 are independently C1-C 10 Alkyl, C3-C 10 A cycloalkyl group or a phenyl group; Each R3 is independently C1-C3 alkyl or hydrogen; m1 and m2 are each independently an integer of 0-300 and are not 0 at the same time; In formula 2: R4 is C1-C 20 of alkylene; n1, n2, and n3 are the same or different, and are each independently an integer of 0-200, and are not 0 at the same time; 2) Adding the terminal epoxy polyether shown in formula 3 to the reaction product mixture obtained in step 1) to react to obtain epoxy polyether-modified silicone oil: Among them, in formula 3: R5 is C1-C 20 of alkylene; R6 is (CH2) n7 O(CH2) n8 ; n4, n5, n6, n7, and n8 are the same or different, and are each independently an integer of 0-200, and are not 0 at the same time.

2. The method according to claim 1, characterized in that In formula 1: Each R, R1, R2 is independently a C1-C6 alkyl, a C3-C6 cycloalkyl or a phenyl group; more preferably a methyl group or a phenyl group; Preferably, each R3 is independently methyl; and / or Preferably, m1 and m2 are each independently an integer of 0-120, and are not both 0; and / or, In formula 2: R4 is a C1-C5 alkylene group, more preferably a methylene group; and / or, Preferably, n1, n2, and n3 are the same or different, and are each independently an integer of 0-100, and are not 0 at the same time; more preferably, they are an integer of 0-70; and / or, In formula 3: R5 is a C1-C5 alkylene group, more preferably a methylene group; and / or, n4, n5, n6, n7, and n8 are the same or different, and are each independently an integer of 0-100, and are not 0 at the same time; more preferably, they are an integer of 0-70.

3. The method according to claim 1 or 2, characterized in that Taking the molar amount of Si-H in the hydrogenated silicone oil shown in Formula 1 as 1, the total molar amount of CH2=CH of the allyl polyether shown in Formula 2 and the allyl epoxy polyether shown in Formula 3 is 0.9-1.6 times the molar amount of Si-H in the hydrogenated silicone oil shown in Formula 1; preferably, the total molar amount of CH2=CH is 1.05-1.4 times the molar amount of Si-H.

4. The method according to any one of claims 1 to 3, characterized in that: The molar amount of CH2=CH in the allyl polyether shown in Formula 2 accounts for 1-15% of the total molar amount of CH2=CH; the molar amount of CH2=CH in the allyl-terminated epoxy polyether shown in Formula 3 accounts for 85-99% of the total molar amount of CH2=CH; Preferably, the molar amount of CH2=CH in the allyl polyether shown in Formula 2 accounts for 5-15% of the total molar amount of CH2=CH; the molar amount of CH2=CH in the allyl-terminated epoxy polyether shown in Formula 3 accounts for 85-95% of the total molar amount of CH2=CH.

5. The method according to any one of claims 1 to 4, characterized in that: The catalyst in step 1) is a platinum-containing compound catalyst; preferably, the platinum-containing compound catalyst is at least one of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex, tetramethyltetravinylcyclotetrasiloxane platinum complex and chloroplatinic acid.

6. The method according to any one of claims 1 to 5, characterized in that: Based on the total mass of the reactants of formula 1, formula 2 and formula 3 in steps 1) and 2), the amount of the platinum-containing compound catalyst is 1-20 ppm; preferably, based on the total mass of the reactants, the amount of the platinum-containing compound catalyst is 5-10 ppm.

7. The method according to any one of claims 1 to 6, characterized in that: The reaction temperature of step 1) is 60-100°C and the reaction time is 0.2-10h; preferably, the reaction temperature is 70-90°C and the reaction time is 0.4-4h.

8. The method according to any one of claims 1 to 7, characterized in that: The reaction temperature of step 2) is 60-100°C and the reaction time is 1-20h; preferably, the reaction temperature is 70-90°C and the reaction time is 1.5-6h.

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