CN113527653A

CN113527653A - Polyether polyol with novel structure and synthesis method thereof

Info

Publication number: CN113527653A
Application number: CN202010314390.5A
Authority: CN
Inventors: 张满
Original assignee: Nanjing Kangzhude Chemical Co ltd
Current assignee: Nanjing Kangzhude Chemical Co ltd
Priority date: 2020-04-20
Filing date: 2020-04-20
Publication date: 2021-10-22

Abstract

The invention relates to polyether polyol with a new structure and a synthesis method thereof, bisphenol A and epoxy resin are reacted for a preset period of time under the catalysis of a specific catalyst, and then the polyether polyol with the new structure is obtained by reacting with epoxide in the presence of the catalyst, wherein the polyether polyol with the new structure comprises the following components:

wherein:

Description

Polyether polyol with novel structure and synthesis method thereof

Technical Field

The invention relates to polyether polyol with a new structure, belonging to the field of high molecular polymers.

Background

The polyether polyol is a variety with the largest use amount and the widest application range in organic polyol compounds. The polyether polyol compound contains ether bond structural units on a main chain, and the end group is hydroxyl.

Polyether polyols are of a wide variety. The hydroxyl number can be classified into polyether diol, polyether triol, polyether tetraol, etc. Classified by the nature of the segments of the polyether backbone, there are polyoxypropylene polyols, polyoxypropylene-oxyethylene polyols, polyoxypropylene-oxytetramethylene polyols, and the like. Classified according to the characteristics of the polyether, there are general polyether polyols, high-activity polyether polyols, polymer polyols, and the like.

Compared with the polyurethane resin synthesized by corresponding polyester polyol, the polyurethane resin synthesized by taking polyether polyol as a matrix has better flexibility, hydrolysis resistance, rebound resilience, low temperature resistance and the like. However, polyurethane resins or flexible foams synthesized from polyethers also have disadvantages, namely, low strength, low load-bearing properties of the foams, and the like. Therefore, the modification of polyether polyols to enhance the strength of the polyurethane products synthesized therefrom has received much attention, and many studies and applications have been made on the modification of polyether polyols, and many materials have been involved. Epoxy resin is one of the materials used for modified polyurethane.

The current research on the correlation between epoxy resins and polyethers focuses mainly on two aspects: the first is the modification of epoxy resin applications with polyethers, with the aim of applying the product to the field of epoxy resin applications. The second type is the property of polyurethane material modified by epoxy resin, and aims to apply the product to the field of polyurethane material.

In the first type of research, the application of polyether to toughening and modifying epoxy resin is mostly focused on the performance improvement of coatings and adhesives. The early research is that polyether is directly added into the formula of epoxy resin, and the polyether does not participate in the reaction, but is used as the function of interpenetrating polymer material networks to modify the performance of the epoxy resin. For example, Luo Yan et al, published in No.3 of 2004 insulating Material, "research on toughening effect of epoxy resin by polyether polyol molecular weight". In recent years, various methods have been used to graft polyethers onto epoxy resins. For example, the polyether polyol is used for toughening and modifying epoxy resin, which is published in the journal of functional polymers, 2010, No. 2, No. 144 and No. 148 of Liushifei et al. The method uses anhydride to react with polyether polyol capped by ethylene oxide to generate polyether polyol containing terminal carboxyl, so as to form epoxy curing agent with polyether group, and then the epoxy curing agent reacts with epoxy bond in epoxy resin to achieve the purpose of modification. There have also been some studies to modify epoxy resins using polyetheramines as curing agents. For example, Liuyu et al, in "aerospace materials Process" supplement 1 in 2014, "research progress on low-temperature mechanical properties of modified epoxy resins". Researchers have also used silicones to modify epoxy resins, such as "chemical modification and development of epoxy resins" published by Yanghei in "scientific information development and economics", volume 16, 21, 2006. In addition, the epoxy resin is modified by phosphate, isocyanate, acrylic acid, acrylate and the like, and is applied to coatings, sealants, adhesives, composite materials and the like. For example, Li Xiangxin et al published "research on polyurethane modified room temperature curing epoxy structural adhesives" at stage 1 of adhesion 2018. Further, the modified epoxy resin used in "self-emulsifiable epoxy resin emulsion for water-based paint and its preparation method" (patent No. CN105713181A) of Shizu et al was simply mixed with an epoxy resin and a polyether polyol.

In combination with the above-mentioned studies, a common feature in the modified products is that epoxy bonds are retained. The modified product may have ester bonds besides epoxy bonds; or an amine ester linkage; or a phosphate ester linkage; or a silicon-oxygen bond, etc.

In the second category of research, much focus has been on the use of various polyurethane materials using acid, anhydride or isocyanate grafted polyethers and epoxy resins. In the aspect of application research of waterborne polyurethane, the waterborne polyurethane is characterized in that epoxy resin, polyether and dicarboxymethylpropionic acid are connected into a polyurethane resin chain by using isocyanate to achieve the aim of modification. For example, the synthesis and performance research of epoxy modified polyurethane polyether type waterborne polyurethane disclosed in the coating industry of 2017 by Royal, et al. WEN Xiu fang et al published in 2005, corrosion science and protection technology, 1 st. For another example, fuhe et al invented a preparation method of modified aqueous polyurethane adhesive, patent No. CN 101003715A. The method is characterized in that epoxy resin is changed into carboxyl-terminated resin by dicarboxymethylpropionic acid, and then the resin and polyether chain are connected into a polyurethane resin chain by isocyanate to achieve the purpose of modification. In the research aspect of non-aqueous polyurethane, the method is characterized in that anhydride or isocyanate is used for grafting epoxy resin and polyether. For example, Caoweihong et al invented "an epoxy resin modified polyisocyanurate high temperature resistant rigid foam and its preparation method" (patent No. CN103059242A) by linking epoxy resin and polyether with isocyanurate. The invention patent of the Stannus et al, "a solvent-free polyurethane composite adhesive and a preparation method thereof" (patent No. CN103013421A), uses anhydride to modify polyether polyol. An in bin and the like, a method used in the research on the preparation and performance of the epoxy resin E51 modified polyurethane elastomer published in the new chemical material 2017 at 2 is to connect the epoxy resin and polyether polyol through isocyanate to achieve the modification purpose. Patent application

Combining the above-mentioned researches, the common feature is that the epoxy resin and polyether polyol are connected by acid or acid anhydride or isocyanate to achieve the purpose of modification. The modified product contains ester bonds or amine ester bonds.

Therefore, from the literature and patents available at present, polyether polyols of the same structure as that of the present invention and related studies have not been found. The invention uses new raw materials and a synthesis method to synthesize a brand new epoxy resin modified polyether polyol structure. The polyether polyol not only successfully introduces epoxy resin into the structure, but also does not contain any ester bond, amine ester bond and other hydrolysable groups in the structure, and completely keeps the basic hydrolysis resistance of the polyether polyol. The polyether polyol is storage stable and can be stored for a long period without deterioration. The polyurethane elastomer has wide application, can be applied to polyurethane coatings, sealants, elastomers and adhesives, and can also be applied to any polyurethane systems such as polyurethane foams and the like.

Disclosure of Invention

A polyether polyol with a new structure and a synthesis method thereof. The structural formula is as follows:

the synthesis method comprises the following steps:

first step of

Second step of

The technical scheme of the invention is as follows:

adding epoxy resin and bisphenol A into a 2-liter high-pressure polymerization kettle, adding a catalyst 1 (manufactured by Nanjing Corp-plast chemical) and reacting for 1-4 hours at 80-180 ℃. Catalyst 2 was then added and replaced with nitrogen twice. Vacuumizing to-0.1 MPa, controlling the temperature at 100-150 ℃, and slowly introducing propylene oxide, ethylene oxide, or tetramethylene oxide, or a mixture of the propylene oxide, the ethylene oxide and the tetramethylene oxide. And aging for 1 hour at 110-150 ℃ after the completion of the introduction, and pumping out redundant epoxide to obtain the product. If refining is needed, adding phosphoric acid for neutralization, then adding deionized water and a magnesium silicate refining agent, and stirring for 1 hour at 70 ℃. The salt was removed by filtration to give the desired product. The hydroxyl value (GBT12008.3-2009), acid value (GBT12008.5-2010), number average molecular weight (GPC method) of the product were measured and the average functionality of the product was calculated.

Detailed Description

The following examples are intended to provide a better understanding of the invention.

Example 1:

e51 epoxy resin DER331 (Dow chemical trade mark) (180.2 g) and bisphenol A (218.9 g) are added into a 2 kg polymerization kettle, and catalyst 1 (made by Nanjing Kangplast chemical) is added to react for 1-4 hours at 80-180 ℃. Then 3 g of catalyst 2 (here potassium hydroxide) was added and the nitrogen was replaced twice. Vacuumizing to-0.1 MPa, controlling the temperature at 110 +/-5 ℃, and slowly introducing 640 g of propylene oxide. After the completion of the reaction, the mixture is aged at 120 ℃ for 1 hour, and residual epoxide is pumped out to obtain the product. 6 grams of 85% phosphoric acid was added to the kettle for neutralization. 35 g of deionized water and 3 g of refining agent are added and stirred for 1 hour at 70 ℃. Filtering to remove salt to obtain refined product of transparent yellowish liquid. The method in the technical scheme is used for detecting various indexes (see table 1).

Example 2:

adding E51 epoxy resin CYD-128 (China petrochemical Baling brand) (93.6 g) and bisphenol A (114 g) into a 2 kg polymerization kettle, adding a catalyst 1 (manufactured by Nanjing Cork plast chemical industry), and reacting at 80-180 ℃ for 1-4 hours. Then 3 g of catalyst 2 (here potassium hydroxide) was added and the nitrogen was replaced twice. Vacuumizing to-0.1 MPa, controlling the temperature at 110 +/-5 ℃, and slowly introducing 840 g of propylene oxide. After completion of the reaction, the mixture was aged at 120 ℃ for 1 hour, and the residual epoxide was taken out to obtain a product which was neutralized with 6 g of 85% phosphoric acid. 35 g of deionized water and 3 g of refining agent are added and stirred for 1 hour at 70 ℃. Filtering to remove salt to obtain refined product of transparent yellowish liquid. The method in the technical scheme is used for detecting various indexes (see table 1).

Example 3:

e51 epoxy resin (Shell brand) EP828(94 g) and bisphenol A (114.5 g) are added into a 2 kg polymerization kettle, catalyst 1 (made by Nanjing Kangplast chemical) is added, and the mixture reacts for 1 to 4 hours at the temperature of 80 to 180 ℃. Then 3 g of catalyst 2 (here potassium hydroxide) was added and the nitrogen was replaced twice. Vacuumizing to-0.1 MPa, controlling the temperature at 110 +/-5 ℃, and slowly introducing 700 g of propylene oxide. After the introduction, 140 g of ethylene oxide were introduced. After aging at 120 ℃ for 1 hour, the residual epoxide was removed by suction to give a product which was neutralized with 6 g of 85% phosphoric acid. 35 g of deionized water and 3 g of refining agent are added and stirred for 1 hour at 70 ℃. Filtering to remove salt to obtain refined product of transparent yellowish liquid. The method in the technical scheme is used for detecting various indexes (see table 1).

Example 4:

adding E51 epoxy resin CYD-128 (China petrochemical Baling brand) (93.6 g) and bisphenol A (114 g) into a 2 kg polymerization kettle, adding a catalyst 1 (manufactured by Nanjing Cork plast chemical industry), and reacting at 80-180 ℃ for 1-4 hours. Then 3 g of catalyst 2 (here potassium hydroxide) was added and the nitrogen was replaced twice. Vacuum-pumping to-0.1 MPa, controlling the temperature at 110 +/-5 ℃, and slowly introducing 840 g of a mixture of ethylene oxide and propylene oxide, wherein the weight ratio of ethylene oxide/propylene oxide is 1: 3. After completion of the reaction, the mixture was aged at 120 ℃ for 1 hour, and the residual epoxide was taken out to obtain a product which was neutralized with 6 g of 85% phosphoric acid. 35 g of deionized water and 3 g of refining agent are added and stirred for 1 hour at 70 ℃. Filtering to remove salt to obtain refined product of transparent yellowish liquid. The method in the technical scheme is used for detecting various indexes (see table 1).

TABLE 1 test index (reaction with different proportions of epoxide and different types of epoxide)

Index (I)	Example 1	Example 2	Example 3	Example 4
					Hydroxyl value (mgKOH/g)	111.9	57.2	56.8	57.0
Acid value (mgKOH/g)	0.08	0.08	0.08	0.08
					Number average molecular weight (Mn)	2035	3930	3985	3947
Epoxy resin content (W/W%)	17.34	8.93	8.97	8.93
					Average functionality (f ═ Mn XOH number/56100)	4.06	4.01	4.03	4.01

Example 5:

e54 epoxy resin CYD-127 (China petrochemical Baling brand) (91.6 g) and bisphenol A (113 g) are added into a 2 kg polymerization kettle, and then catalyst 1 (made by Nanjing Cork plast chemical) is added to react for 1-4 hours at 80-180 ℃. Then 3 g of catalyst 2 (here potassium hydroxide) was added and the nitrogen was replaced twice. Vacuumizing to-0.1 MPa, controlling the temperature at 110 +/-5 ℃, and slowly introducing 850 g of propylene oxide. After the completion of the reaction, the mixture is aged at 120 ℃ for 1 hour, and residual epoxide is pumped out to obtain the product. 6 g of 85% phosphoric acid was added for neutralization. 35 g of deionized water and 3 g of refining agent are added and stirred for 1 hour at 70 ℃. Filtering to remove salt to obtain refined product of transparent yellowish liquid. The method in the technical scheme is used for detecting each index (see table 2).

Example 6:

adding E44 epoxy resin CYD-144 (China petrochemical Balng brand) (92.3 g) and bisphenol A (105.1 g) into a 2 kg polymerization kettle, adding a catalyst 1 (manufactured by Nanjing Cork-Plastic chemical industry), and reacting at 80-180 ℃ for 1-4 hours. Then 3 g of catalyst 2 (here potassium hydroxide) was added and the nitrogen was replaced twice. Vacuumizing to-0.1 MPa, controlling the temperature at 110 +/-5 ℃, and slowly introducing 780 g of propylene oxide. After the completion of the reaction, the mixture is aged at 120 ℃ for 1 hour, and residual epoxide is pumped out to obtain the product. 6 g of 85% phosphoric acid was added for neutralization. 35 g of deionized water and 3 g of refining agent are added and stirred for 1 hour at 70 ℃. Filtering to remove salt to obtain refined product of transparent yellowish liquid. The method in the technical scheme is used for detecting each index (see table 2).

TABLE 2 test indexes (reaction with different types of epoxy resins)

Index (I)	Example 5	Example 6
			Hydroxyl value (mgKOH/g)	56.4	57.0
Acid value (mgKOH/g)	0.07	0.08
			Number average molecular weight (Mn)	3978	4055
Average functionality (f ═ Mn XOH number/56100)	4.00	4.12

Example 7:

200 g of the product from example 1 were charged with 0.1 g of bimetallic catalyst DMC and purged with nitrogen twice. Vacuumizing to-0.1 MPa, controlling the temperature at 140 +/-5 ℃, and slowly introducing 200 g of propylene oxide. After the completion of the reaction, the reaction mixture was aged at 140 ℃ for 1 hour, and the residual epoxide was removed by suction to obtain a colorless transparent liquid product. The method in the technical scheme is used for detecting each index (see table 3).

Example 8:

200 g of the product from example 1 were charged with 0.1 g of bimetallic catalyst DMC and purged with nitrogen twice. Vacuum is pumped to-0.1 MPa, the temperature is controlled at 140 +/-5 ℃, 200 g of propylene oxide is slowly pumped in, and then 200 g of mixed alkane is pumped in (ethylene oxide/propylene oxide is 1: 1). After the completion of the reaction, the reaction mixture was aged at 140 ℃ for 1 hour, and the residual epoxide was removed by suction to obtain a colorless transparent liquid product. The method in the technical scheme is used for detecting each index (see table 3).

Example 9:

200 g of the product from example 1 were charged with 0.1 g of bimetallic catalyst DMC and purged with nitrogen twice. Vacuumizing to-0.1 MPa, controlling the temperature at 140 +/-5 ℃, and slowly introducing 800 g of propylene oxide. After the completion of the reaction, the reaction mixture was aged at 140 ℃ for 1 hour, and the residual epoxide was removed by suction to obtain a colorless transparent liquid product. The method in the technical scheme is used for detecting each index (see table 3).

TABLE 3 test indexes (epoxide grafted with bimetallic catalyst)

Index (I)	Example 7	Example 8	Example 9
				Hydroxyl value (mgKOH/g)	56.0	27.9	22.2
Acid value (mgKOH/g)	0.05	0.04	0.04
				Number average molecular weight (Mn)	4067	8134	10260
Average functionality (f ═ Mn XOH number/56100)	4.06	4.06	4.06

Wherein, the results of example 1 and example 2 show that the polyether polyol with different molecular weights can be obtained by adding different amounts of epoxide. The results of examples 2 and 3 show that the present invention can be used with different commercial grades of E51 epoxy resin to obtain polyether polyols of the same molecular weight. The results of examples 2, 3 and 4 show that the present invention can incorporate different types of epoxides and mixtures thereof.

The results of examples 5 and 6 show that the present invention allows the synthesis of polyether polyols of the structure described to be carried out with epoxy resins of different molecular weights.

The results of examples 7, 8 and 9 show that secondary chain extension using bimetallic catalysts is also possible to obtain products of different molecular weights. It is recommended to prepare polyether polyols of this structure having a high molecular weight and a low degree of unsaturation by this method.

The above discussion is for illustrative purposes only and is not meant to limit the scope of the invention.

Claims

1. A polyether polyol with a new structure and a synthesis method thereof are characterized in that: a typical structural formula is:

wherein:

a typical synthesis reaction is as follows:

first step of

Second step of

2. The polyether polyol of new structure and its synthesis as claimed in claim 1, features that: r1; r2; r3; r4; r5 are all hydroxyl-terminated groups.

3. The polyether polyol of new structure and its synthesis as claimed in claim 1, features that: the structure does not contain ester bonds.

4. The polyether polyol of new structure and its synthesis as claimed in claim 1, features that: m is 0-500; k is 0-500; m + k ≠ 0.

5. The polyether polyol of new structure and its synthesis as claimed in claim 1, features that: m1 is 0-100; m2 is 0-100; m3 is 0-100; m4 is 0-100; m5 is 0-100; k1 is 0-100; k2 is 0 to 100; k3 is 0-100; k4 is 0-100; k5 is 0-100.

6. The polyether polyol of new structure and its synthesis as claimed in claim 1, features that: the present invention uses bisphenol a addition epoxy resins but is not limited to bisphenol a. The method is also suitable for diphenols such as hydroquinone, resorcinol and the like.

7. The polyether polyol of new structure and its synthesis as claimed in claim 1, features that: the molecular weight of the epoxy resin is 100-1500, or the mixed resin with various molecular weights.

8. The polyether polyol of new structure and its synthesis as claimed in claim 7, features that: bisphenol a epoxy resins are used in the present invention, but are not limited to bisphenol a epoxy resins. The same applies to all glycidyl ether epoxy resins.

9. The polyether polyol of new structure and its synthesis as claimed in claim 1, features that: the epoxide is pure propylene oxide; or pure ethylene oxide; or a mixture of propylene oxide and ethylene oxide in any proportion.

10. The polyether polyol of new structure and its synthesis as claimed in claim 9, wherein: the present invention uses propylene oxide and ethylene oxide as an adduct, but is not limited to propylene oxide and ethylene oxide. The same applies to the epoxides which can be added by ring-opening such as tetramethylene oxide and tetrahydrofuran.