A kind of ultra-high molecular weight methyl bromide epoxy resin and its preparation method and application

Abstract

The present invention belongs to the technical field of organic synthesis, and specifically relates to an ultra-high molecular weight methyl bromide epoxy resin, a preparation method thereof, and an application thereof. The preparation method provided by the present invention has simple steps, is easy to operate, and is convenient for industrial production. The ultra-high molecular weight methyl bromide epoxy resin obtained can be used for the modification of resins such as PBT and PET, and has good miscibility with other resins. Compared with the traditional high molecular weight brominated epoxy resin synthesized with epichlorohydrin and tetrabromobisphenol A, the ultra-high molecular weight methyl bromide epoxy resin provided by the present invention has good miscibility with other resins, better UV resistance and weather resistance, good mechanical and electrical properties, a melting point between 147 and 153°C, excellent physical and chemical properties, and a wider range of applications. The ultra-high molecular weight methyl bromide epoxy resin provided by the present invention is particularly suitable for the modification of PBT, PET, or flame-retardant hair. The amount used in flame-retardant hair is reduced by more than 20%, with significant economic benefits and further improved product quality.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and particularly relates to an ultra-high molecular weight methyl bromide epoxy resin and a preparation method and application thereof. Background Art

[0002] The weight-average molecular weight of high molecular weight brominated epoxy resin synthesized with epichlorohydrin is usually between 15,000 and 40,000, and is mainly used in the electronics, automotive, and household appliance industries.

[0003] Since the melting point of high molecular weight brominated epoxy resin is relatively high, generally when the molecular weight exceeds 30,000, its melting point is between 155 and 162°C, and a large amount of heat is generated during the polymerization process, making temperature control very difficult. The synthesized high molecular weight brominated epoxy resin has a relatively wide molecular weight distribution and poor miscibility with resins such as PBT, PET or nylon, making it difficult to use for the modification of hair, fibers, nylon or PET resins.

[0004] Chinese invention publication CN1648148A discloses a method for producing a brominated epoxy resin. Using epichlorohydrin and tetrabromobisphenol A as raw materials, the resulting high-molecular-weight brominated epoxy resin has a molecular weight of 4,000 to 30,000. This improves the recovery rate of epichlorohydrin, but the method still exhibits common drawbacks of high-molecular-weight brominated epoxy resins, such as poor miscibility with resins such as PBT, PET, or nylon, leading to problems such as clogging, breakage, and discoloration during the spinning process.

[0005] Therefore, how to provide a brominated epoxy resin that has good miscibility with resins is a problem that needs to be solved urgently by those skilled in the art. Summary of the Invention

[0006] The purpose of the present invention is to provide an ultra-high molecular weight methyl bromide epoxy resin and its preparation method and application. The ultra-high molecular weight methyl bromide epoxy resin provided by the present invention has a weight-average molecular weight of not less than 40,000 and has good miscibility with other resins.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] The present invention provides a method for preparing an ultra-high molecular weight methyl bromide epoxy resin, comprising the following steps:

[0009] (1) Methyl epichlorohydrin, the first portion of tetrabromobisphenol A and a crown ether catalyst are mixed to perform a ring-opening reaction to obtain an intermediate product, brominated bisphenol A chlorohydrin ether, with the molecular formula C 23 H 26 Br4Cl2O4, the structural formula is shown in Formula I:

[0010]

[0011] (2) The intermediate product, toluene and liquid alkali are mixed to carry out a ring-closing reaction to obtain a low molecular weight methyl bromide epoxy resin with a molecular formula of C 23 H 24 Br4O4, molecular weight is 684, and the structural formula is shown in Formula II:

[0012]

[0013] (3) mixing the low molecular weight methyl bromide epoxy resin, the second portion of tetrabromobisphenol A and a composite organic catalyst to carry out a polymerization reaction to obtain an ultra-high molecular weight methyl bromide epoxy resin.

[0014] Preferably, the mass ratio of the methyl epichlorohydrin to the first portion of tetrabromobisphenol A is 200-1000:500;

[0015] The mass ratio of the methyl epichlorohydrin to the crown ether catalyst is 200-1000:1-4;

[0016] The mass ratio of methyl epichlorohydrin to toluene is 200-1000:400;

[0017] The mass ratio of methyl epichlorohydrin to liquid caustic soda is 200-1000:250-450;

[0018] The concentration of the liquid caustic soda is 28-32 wt %.

[0019] Preferably, the mass ratio of the low molecular weight methyl brominated epoxy resin to the second portion of tetrabromobisphenol A is 255:195-205;

[0020] The mass ratio of the low molecular weight methyl bromide epoxy resin to the composite organic catalyst is 255:0.8-1.5.

[0021] Preferably, the molecular formula of the crown ether catalyst is C 20 H 24 O6, the structural formula is shown in Formula III:

[0022]

[0023] Preferably, the composite organic catalyst is a crown ether catalyst and an organic catalyst; the organic catalyst includes one or more of benzyltriphenylphosphine bromide, hexadecyltrimethylammonium bromide, triphenylphosphine and tetrabutylammonium chloride.

[0024] Preferably, the mass ratio of the crown ether catalyst to the organic catalyst in the composite organic catalyst is 1:0.8-1.2.

[0025] Preferably, the temperature of the ring-opening reaction is 105-110° C., the holding time is 4-4.5 hours, and the ring-opening reaction is carried out under nitrogen protection;

[0026] The temperature of the ring-closing reaction is 85-90° C., and the insulation time is 5.5-6.5 hours.

[0027] Preferably, the polymerization reaction temperature is 180-210° C., and the holding time is 60-80 minutes; and the polymerization reaction is carried out under nitrogen protection.

[0028] The present invention also provides an ultra-high molecular weight methyl bromide epoxy resin obtained by the preparation method described in the above scheme. The ultra-high molecular weight methyl bromide epoxy resin has a weight average molecular weight of 40,000 to 60,000, an epoxy value of 0.0033 to 0.005 eq / 100 g, and a melting point of 147 to 153° C. The structural formula of the ultra-high molecular weight methyl bromide epoxy resin is shown in Formula IV:

[0029]

[0030] The value of n ranges from 32 to 48.

[0031] The present invention also provides the use of the ultra-high molecular weight methyl bromide epoxy resin described in the above solution in resin modification.

[0032] The present invention provides a method for preparing an ultra-high molecular weight methyl bromide epoxy resin. The method uses a crown ether catalyst to synthesize a low molecular weight methyl bromide epoxy resin having an epoxy equivalent weight of 342 to 350. The low molecular weight methyl bromide epoxy resin is then combined with tetrabromobisphenol A and a composite organic catalyst to synthesize an ultra-high molecular weight methyl bromide epoxy resin. The preparation method provided by the present invention is simple, easy to operate, and amenable to industrial production. The resulting ultra-high molecular weight methyl bromide epoxy resin has a higher molecular weight. Because the ultra-high molecular weight methyl bromide epoxy resin provided by the present invention contains a large number of methyl side chains, it has better compatibility with other resins.

[0033] The present invention also provides an ultra-high molecular weight methyl bromide epoxy resin obtained by the preparation method described in the above scheme. Compared to conventional high molecular weight brominated epoxy resins synthesized using epichlorohydrin and tetrabromobisphenol A, the ultra-high molecular weight methyl bromide epoxy resin provided by the present invention has good compatibility with other resins, improved UV and weather resistance, excellent mechanical and electrical properties, a melting point between 147 and 153°C, excellent physical and chemical properties, and a wider range of applications.

[0034] The present invention also provides the use of the ultra-high molecular weight methyl bromide epoxy resin described in the above embodiment in resin modification. The ultra-high molecular weight methyl bromide epoxy resin provided by the present invention is particularly suitable for modifying PBT, PET, and flame-retardant hair. The amount of methyl bromide epoxy resin used in flame-retardant hair can be reduced by more than 20%, resulting in significant economic benefits and further improved product quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0036] Figure 1 This is an appearance diagram of the ultra-high molecular weight methyl bromide epoxy resin prepared in Example 1 of the present invention;

[0037] Figure 2 This is an appearance diagram of the flame-retardant hair prepared in Application Example 1 of the present invention;

[0038] Figure 3 This is a diagram showing the appearance of flame-retardant hair made from the commercially available FR-2400 high molecular weight brominated epoxy resin synthesized from epichlorohydrin and tetrabromobisphenol A;

[0039] Figure 4 This is a molecular weight distribution curve of the ultra-high molecular weight methyl bromide epoxy resin prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0040] The present invention provides a method for preparing an ultra-high molecular weight methyl bromide epoxy resin, comprising the following steps:

[0041] (1) Methyl epichlorohydrin, the first portion of tetrabromobisphenol A and a crown ether catalyst are mixed to perform a ring-opening reaction to obtain an intermediate product, brominated bisphenol A chlorohydrin ether, with the molecular formula C 23 H 26 Br4Cl2O4, the structural formula is shown in Formula I:

[0042]

[0043] (2) The intermediate product, toluene and liquid alkali are mixed to carry out a ring-closing reaction to obtain a low molecular weight methyl bromide epoxy resin with a molecular formula of C 23 H 24 Br4O4, molecular weight is 684, and the structural formula is shown in Formula II:

[0044]

[0045] (3) mixing the low molecular weight methyl bromide epoxy resin, the second portion of tetrabromobisphenol A and a composite organic catalyst to carry out a polymerization reaction to obtain an ultra-high molecular weight methyl bromide epoxy resin.

[0046] The present invention mixes methyl epichlorohydrin, the first portion of tetrabromobisphenol A and a crown ether catalyst to carry out a ring-opening reaction to obtain an intermediate product, brominated bisphenol A chlorohydrin ether, with a molecular formula of C 23 H 26 Br4Cl2O4, the structural formula is shown in Formula I. In the present invention, the molecular formula of the crown ether catalyst is C 20 H 24 O6, the structural formula is shown in Formula III:

[0047]

[0048] In the present invention, the mass ratio of the methyl epichlorohydrin and the first portion of tetrabromobisphenol A is preferably 200-1000:500, more preferably 400-900:500, and further preferably 700-900:500; the mass ratio of the methyl epichlorohydrin and the crown ether catalyst is preferably 200-1000:1-4, more preferably 400-900:1.5-4, and further preferably 700-900:1.5-2; the temperature of the ring-opening reaction is preferably 105-110° C., more preferably 107-109° C., the holding time is preferably 3.5-4.5 hours, more preferably 4 hours, and the ring-opening reaction is preferably carried out under nitrogen protection; the reaction equation of the ring-opening reaction is as follows:

[0049]

[0050] In the present invention, after the ring-opening reaction, the obtained intermediate product system is preferably subjected to reduced pressure distillation to obtain the intermediate product brominated bisphenol A chlorohydrin ether; the temperature of the reduced pressure distillation is preferably 135-140° C., more preferably 137-139° C., the vacuum degree is preferably -0.092-0.098 MPa, more preferably -0.095 MPa, and the reduced pressure distillation is performed until no effluent is produced; the present invention removes excess methyl epichlorohydrin by reduced pressure distillation.

[0051] After obtaining the intermediate product, the present invention mixes the intermediate product, toluene and liquid alkali to carry out a ring-closing reaction to obtain a low molecular weight methyl bromide epoxy resin with a molecular formula of C 23 H 24Br4O4, molecular weight 684, structural formula as shown in formula II. In the present invention, the mass ratio of methyl epichlorohydrin and toluene is preferably 200-1000:400, more preferably 400-900:400, further preferably 700-900:400; the mass ratio of methyl epichlorohydrin and liquid caustic soda is preferably 200-1000:250-450, more preferably 400-900:250-450, further preferably 700-900:300-350; the concentration of liquid caustic soda is preferably 28-32wt%, more preferably 30wt%; the temperature of the ring-closure reaction is preferably 85-90°C, more preferably 87-89°C, and the holding time is preferably 5.5-6.5 hours, more preferably 6 hours; the reaction equation of the ring-closure reaction is as follows:

[0052]

[0053] In the present invention, after the ring-closure reaction, the obtained product is preferably washed to neutrality and then distilled under reduced pressure; the washing agent is preferably deionized water; the temperature of the deionized water is preferably 85-90°C, more preferably 87-89°C; the temperature of the reduced pressure distillation is preferably 130-135°C, more preferably 132-134°C, and the vacuum degree is preferably -0.092-0.098MPa, more preferably -0.095MPa. In the present invention, the intermediate product, toluene and liquid caustic soda are preferably mixed by cooling the intermediate product to 90°C under nitrogen protection, then adding toluene and stirring evenly, and finally adding liquid caustic soda; the stirring time is preferably 20 minutes.

[0054] After obtaining the low molecular weight methyl bromide epoxy resin, the present invention mixes the low molecular weight methyl bromide epoxy resin, the second portion of tetrabromobisphenol A and a composite organic catalyst to carry out a polymerization reaction to obtain an ultra-high molecular weight methyl bromide epoxy resin. In the present invention, the composite organic catalyst is preferably a crown ether catalyst and an organic catalyst; the organic catalyst preferably includes one or more of benzyltriphenylphosphine bromide, hexadecyltrimethylammonium bromide, triphenylphosphine and tetrabutylammonium chloride; the mass ratio of the crown ether catalyst and the organic catalyst in the composite organic catalyst is preferably 1:0.8 to 1.2, more preferably 1:1; when the composite organic catalyst is a crown ether catalyst, benzyltriphenylphosphine bromide and hexadecyltrimethylammonium bromide, the mass ratio of the crown ether catalyst, benzyltriphenylphosphine bromide and hexadecyltrimethylammonium bromide is preferably 2:1:1; the mass ratio of the low molecular weight methyl bromide epoxy resin to the second portion of tetrabromobisphenol A is preferably 2:5. 5:195-205, more preferably 255:197-202, further preferably 255:200; the mass ratio of the low molecular weight methyl bromide epoxy resin to the composite organic catalyst is preferably 255:0.8-1.5, more preferably 255:0.9-1.2, further preferably 255:1.0; the temperature of the polymerization reaction is preferably 180-210°C, more preferably 190-200°C, and the holding time is preferably 60-80 minutes, more preferably 70 minutes; the polymerization reaction is preferably carried out under nitrogen protection; the polymerization reaction is preferably terminated after the acid value of the polymerization reaction system reaches 0.3 mgkoh / g; the reaction equation of the polymerization reaction is as follows:

[0055]

[0056] The present invention also provides an ultra-high molecular weight methyl bromide epoxy resin obtained by the preparation method described in the above scheme. The ultra-high molecular weight methyl bromide epoxy resin has a weight average molecular weight of 40,000 to 60,000, an epoxy value of 0.0033 to 0.005 eq / 100 g, and a melting point of 147 to 153° C. The structural formula of the ultra-high molecular weight methyl bromide epoxy resin is shown in Formula IV:

[0057]

[0058] The value of n ranges from 32 to 48.

[0059] In the present invention, the weight average molecular weight of the ultra-high molecular weight methyl brominated epoxy resin is preferably 45,000 to 55,000, more preferably 50,000, the number average molecular weight is preferably 22,000 to 26,000, more preferably 24,000, the melting point is preferably 150° C., the acid value is preferably not higher than 0.3 mgkoh / g, more preferably 0.1 to 0.3 mgkoh / g, the chromaticity is preferably not more than 50 (10%, APHA), and the bromine content is preferably 51.5 to 52.0%, more preferably 51.8%.

[0060] The present invention also provides the use of the ultra-high molecular weight methyl bromide epoxy resin described in the above solution in resin modification.

[0061] In the present invention, the ultra-high molecular weight methyl bromide epoxy resin is suitable for modifying other resins, and is particularly suitable for modifying flame-retardant hair (containing resin in its ingredients); the use of the ultra-high molecular weight methyl bromide epoxy resin in flame-retardant hair preferably comprises the following steps: mixing PBT resin, PET resin, ultra-high molecular weight methyl bromide epoxy resin, antimony trioxide and a toughening agent, and then screw-extruding and granulating to obtain a flame-retardant hair masterbatch; and heating the flame-retardant hair masterbatch and then spinning it to obtain the flame-retardant hair.

[0062] In the present invention, the mass ratio of the PBT resin to the PET resin is preferably 1:1; the mass ratio of the PBT resin to the ultra-high molecular weight methyl bromide epoxy resin is preferably 5:1; the mass ratio of the PBT resin to antimony trioxide is preferably 50:3.3; and the mass ratio of the PBT resin to the toughening agent is preferably 50:2.5. The screw extrusion device is preferably a twin-screw extruder; and the spinning device is preferably a spinning machine. Compared to the epoxy resin synthesized from epichlorohydrin and tetrabromobisphenol A, which is added in an amount of over 13% in flame-retardant hair, the ultra-high molecular weight methyl bromide epoxy resin provided by the present invention is added in an amount of under 10% in flame-retardant hair, a relative reduction of over 20% ((13% - 10%) / 13%). The flame retardant effect reaches UL94-V0, the color brightness of the flame-retardant hair is significantly improved, and the physical and chemical properties are superior.

[0063] In order to further illustrate the present invention, the scheme of the present invention is described in detail below with reference to the accompanying drawings and embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0064] In a specific embodiment of the present invention, tetrabromobisphenol A is purchased from Albemarle, USA, and the content of tetrabromobisphenol A is 99.80%, and the bromine content is 58.80%.

[0065] Example 1

[0066] First, a low molecular weight methyl bromide epoxy resin is prepared, comprising the following components in parts by weight:

[0067]

[0068] The preparation method of low molecular weight methyl bromide epoxy resin comprises the following steps:

[0069] (1) putting methyl epichlorohydrin, tetrabromobisphenol A and crown ether catalyst into a reactor;

[0070] (2) heating under nitrogen protection and maintaining the ring-opening reaction at 106°C for 4 hours;

[0071] (3) Excess methyl epichlorohydrin was distilled under reduced pressure to 136°C, with a vacuum degree of -0.095 MPa, and no effluent was produced;

[0072] (4) Fill with nitrogen, cool to 90°C, add toluene, and stir for 20 minutes;

[0073] (5) adding 30% liquid caustic soda and carrying out the ring-closure reaction at 86°C for 6 hours;

[0074] (6) Wash with 90°C deionized water until neutral;

[0075] (7) heating and reducing the pressure to distill the obtained low molecular weight methyl bromide epoxy resin until the temperature reaches 131° C. and the vacuum degree is -0.095 MPa;

[0076] (8) The epoxy value of the low molecular weight methyl bromide epoxy resin was tested to be 0.291, and the resin was metered into a polymerization reactor to prepare an ultrahigh molecular weight methyl bromide epoxy resin;

[0077] Second, prepare an ultra-high molecular weight methyl bromide epoxy resin, including the following components in parts by weight:

[0078] 255 parts of low molecular weight methyl bromide epoxy resin;

[0079] 197 parts of tetrabromobisphenol A;

[0080] 1.0 part of composite organic catalyst;

[0081] The mass ratio of the crown ether catalyst, benzyltriphenylphosphonium bromide and hexadecyltrimethylammonium bromide in the composite organic catalyst is 2:1:1.

[0082] The preparation method of ultra-high molecular weight methyl bromide epoxy resin comprises the following steps:

[0083] (1) adding low molecular weight methyl bromide epoxy resin, tetrabromobisphenol A and composite organic catalyst into a reaction kettle;

[0084] (2) stirring and heating under nitrogen protection, reacting at 192°C for 70 minutes;

[0085] (3) taking a sample to measure the acid value, and discharging the material when the acid value is 0.3 mgkoh / g to obtain an ultra-high molecular weight methyl bromide epoxy resin;

[0086] The quality indicators of the ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0087] The weight average molecular weight is 50102, the melting point is 149.5℃, the acid value is 0.2mgkoh / g, the color is (10%, APHA) 40, the bromine content is 51.85%, and the appearance is as follows Figure 1 shown.

[0088] Example 2

[0089] The preparation method of low molecular weight methyl bromide epoxy resin and ultra-high molecular weight methyl bromide epoxy resin is the same as that in Example 1, except that:

[0090] 255 parts of low molecular weight methyl bromide epoxy resin;

[0091] 198 parts of tetrabromobisphenol A;

[0092] 1.1 parts of composite organic catalyst;

[0093] The quality indicators of the obtained ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0094] The weight average molecular weight is 50900, the melting point is 149.6°C, the acid value is 0.22 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.85%.

[0095] Example 3

[0096] The preparation method of low molecular weight methyl bromide epoxy resin and ultra-high molecular weight methyl bromide epoxy resin is the same as that in Example 1, except that:

[0097] 255 parts of low molecular weight methyl bromide epoxy resin;

[0098] 199 parts of tetrabromobisphenol A;

[0099] 1.2 parts of composite organic catalyst;

[0100] The quality indicators of the obtained ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0101] The weight average molecular weight is 51900, the melting point is 149.6°C, the acid value is 0.23 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.86%.

[0102] Example 4

[0103] The preparation method of low molecular weight methyl bromide epoxy resin and ultra-high molecular weight methyl bromide epoxy resin is the same as that in Example 1, except that:

[0104] 255 parts of low molecular weight methyl bromide epoxy resin;

[0105] 204 parts of tetrabromobisphenol A;

[0106] 1.2 parts of composite organic catalyst;

[0107] The quality indicators of the obtained ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0108] The weight average molecular weight is 53600, the melting point is 150.3°C, the acid value is 0.25 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.87%.

[0109] Example 5

[0110] The preparation method of low molecular weight methyl bromide epoxy resin and ultra-high molecular weight methyl bromide epoxy resin is the same as that in Example 1, except that:

[0111] 255 parts of low molecular weight methyl bromide epoxy resin;

[0112] 205 parts of tetrabromobisphenol A;

[0113] 1.4 parts of composite organic catalyst;

[0114] The quality indicators of the obtained ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0115] The weight average molecular weight is 56120, the melting point is 152.2° C., the acid value is 0.25 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.88%.

[0116] Example 6

[0117] First, a low molecular weight methyl bromide epoxy resin is prepared, comprising the following components in parts by weight:

[0118]

[0119] The preparation method of the low molecular weight methyl bromide epoxy resin comprises the following steps:

[0120] (1) putting methyl epichlorohydrin, tetrabromobisphenol A and crown ether catalyst into a reactor;

[0121] (2) heating under nitrogen protection and maintaining the ring-opening reaction at 109°C for 4 hours;

[0122] (3) Excess methyl epichlorohydrin was distilled under reduced pressure to 139°C, with a vacuum degree of -0.095 MPa and no effluent;

[0123] (4) Fill with nitrogen, cool to 90°C, add toluene, and stir for 20 minutes;

[0124] (5) adding 30% liquid caustic soda and carrying out the ring-closure reaction at 89°C for 6 hours;

[0125] (6) Wash with 90°C deionized water until neutral;

[0126] (7) heating and reducing pressure to distill the obtained low molecular weight methyl bromide epoxy resin until the temperature reaches 135° C. and the vacuum degree reaches -0.095 MPa;

[0127] (8) The epoxy value of the low molecular weight methyl bromide epoxy resin was tested to be 0.292, and the resin was metered into a polymerization reactor to prepare an ultrahigh molecular weight methyl bromide epoxy resin;

[0128] Second, synthesize an ultra-high molecular weight methyl bromide epoxy resin, including the following components in parts by weight:

[0129] 255 parts of low molecular weight methyl bromide epoxy resin;

[0130] 197 parts of tetrabromobisphenol A;

[0131] 1.0 part of composite organic catalyst;

[0132] The mass ratio of the crown ether catalyst, benzyltriphenylphosphonium bromide and hexadecyltrimethylammonium bromide in the composite organic catalyst is 2:1:1.

[0133] The preparation method of the ultra-high molecular weight methyl bromide epoxy resin comprises the following steps:

[0134] (1) adding low molecular weight methyl bromide epoxy resin, tetrabromobisphenol A and composite organic catalyst into a reaction kettle;

[0135] (2) stirring and heating under nitrogen protection, and polymerizing at 206°C for 76 minutes;

[0136] (3) taking a sample to measure the acid value, and discharging the material when the acid value reaches 0.3 mgkoh / g to obtain an ultra-high molecular weight methyl bromide epoxy resin;

[0137] The quality indicators of the ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0138] The weight average molecular weight is 50200, the melting point is 150.6°C, the acid value is 0.2 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.86%.

[0139] Example 7

[0140] The preparation method of low molecular weight methyl bromide epoxy resin and ultra-high molecular weight methyl bromide epoxy resin is the same as that in Example 6, except that:

[0141] 255 parts of low molecular weight methyl bromide epoxy resin;

[0142] 198 parts of tetrabromobisphenol A;

[0143] 1.1 parts of composite organic catalyst;

[0144] The quality indicators of the obtained ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0145] The weight average molecular weight is 51,000, the melting point is 150.7° C., the acid value is 0.21 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.86%.

[0146] Example 8

[0147] The preparation method of low molecular weight methyl bromide epoxy resin and ultra-high molecular weight methyl bromide epoxy resin is the same as that in Example 6, except that:

[0148] 255 parts of low molecular weight methyl bromide epoxy resin;

[0149] 199 parts of tetrabromobisphenol A;

[0150] 1.2 parts of composite organic catalyst;

[0151] The quality indicators of the obtained ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0152] The weight average molecular weight is 51950, the melting point is 151.8°C, the acid value is 0.22 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.88%.

[0153] Example 9

[0154] The preparation method of low molecular weight methyl bromide epoxy resin and ultra-high molecular weight methyl bromide epoxy resin is the same as that in Example 6, except that:

[0155] 255 parts of low molecular weight methyl bromide epoxy resin;

[0156] 204 parts of tetrabromobisphenol A;

[0157] 1.2 parts of composite organic catalyst;

[0158] The quality indicators of the obtained ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0159] The weight average molecular weight is 53820, the melting point is 151.3° C., the acid value is 0.25 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.88%.

[0160] Example 10

[0161] The preparation method of low molecular weight methyl bromide epoxy resin and ultra-high molecular weight methyl bromide epoxy resin is the same as that in Example 6, except that:

[0162] 255 parts of low molecular weight methyl bromide epoxy resin;

[0163] 205 parts of tetrabromobisphenol A;

[0164] 1.4 parts of composite organic catalyst;

[0165] The quality indicators of the obtained ultra-high molecular weight methyl bromide epoxy resin are as follows:

[0166] The weight average molecular weight is 56300, the melting point is 152.8°C, the acid value is 0.25 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.88%.

[0167] Comparative Example 1

[0168] First, a low molecular weight methyl bromide epoxy resin is prepared, comprising the following components in parts by weight:

[0169]

[0170]

[0171] The preparation method of the low molecular weight methyl bromide epoxy resin comprises the following steps:

[0172] (1) putting methyl epichlorohydrin, tetrabromobisphenol A and crown ether catalyst into a reactor;

[0173] (2) heating under nitrogen protection and maintaining the ring-opening reaction at 106°C for 4 hours;

[0174] (3) Excess methyl epichlorohydrin was distilled under reduced pressure to 137°C, with a vacuum degree of -0.095 MPa and no effluent;

[0175] (4) Fill with nitrogen, cool to 90°C, add toluene, and stir for 20 minutes;

[0176] (5) adding 30% liquid caustic soda and carrying out the ring-closure reaction at 87°C for 6 hours;

[0177] (6) Wash with 90°C deionized water until neutral;

[0178] (7) heating and reducing pressure to distill the obtained low molecular weight methyl bromide epoxy resin until the temperature reaches 133° C. and the vacuum degree reaches -0.095 MPa;

[0179] (8) The epoxy value of the low molecular weight methyl bromide epoxy resin was tested to be 0.291, and the resin was metered into a polymerization reactor to prepare a high molecular weight methyl bromide epoxy resin;

[0180] Second, a high molecular weight methyl bromide epoxy resin was prepared, comprising the following components in parts by weight:

[0181] 255 parts of low molecular weight methyl bromide epoxy resin;

[0182] 197 parts of tetrabromobisphenol A;

[0183] 1.8 parts of composite organic catalyst;

[0184] The mass ratio of the crown ether catalyst, benzyltriphenylphosphonium bromide and hexadecyltrimethylammonium bromide in the composite organic catalyst is 2:1:1.

[0185] The preparation method of the high molecular weight methyl bromide epoxy resin comprises the following steps:

[0186] (1) adding low molecular weight methyl bromide epoxy resin, tetrabromobisphenol A and composite organic catalyst into a reaction kettle;

[0187] (2) stirring and heating under nitrogen protection, and polymerizing at 198°C for 72 minutes;

[0188] (3) taking a sample to measure the acid value, and discharging the material when the acid value is 0.3 mgkoh / g to obtain a high molecular weight methyl bromide epoxy resin;

[0189] The quality indicators of the obtained high molecular weight methyl bromide epoxy resin are as follows:

[0190] The weight average molecular weight is 39,000, the melting point is 149.5° C., the acid value is 0.4 mgkoh / g, the color is (10%, APHA) 40, and the bromine content is 51.86%.

[0191] Since the amount of composite organic catalyst used was too much and the polymerization speed was too fast, the molecular weight and acid value of the obtained methyl bromide epoxy resin were unqualified.

[0192] Comparative Example 2

[0193] The preparation method of the low molecular weight methyl bromide epoxy resin and the high molecular weight methyl bromide epoxy resin is the same as that of Comparative Example 1, except that:

[0194] 255 parts of low molecular weight methyl bromide epoxy resin;

[0195] 197 parts of tetrabromobisphenol A;

[0196] 1.3 parts of benzyltriphenylphosphonium bromide;

[0197] The quality indicators of the obtained high molecular weight methyl bromide epoxy resin are as follows:

[0198] The weight average molecular weight is 35600, the melting point is 147.6°C, the acid value is 1.20 mgkoh / g, the color is (10%, APHA) 50, and the bromine content is 51.80%.

[0199] Since the catalytic effect of benzyltriphenylphosphonium bromide is poor, the molecular weight and acid value of the synthesized methyl bromide epoxy resin are unqualified.

[0200] Comparative Example 3

[0201] The preparation method of the low molecular weight methyl bromide epoxy resin and the high molecular weight methyl bromide epoxy resin is the same as that of Comparative Example 1, except that:

[0202] 255 parts of low molecular weight methyl bromide epoxy resin;

[0203] 197 parts of tetrabromobisphenol A;

[0204] 1.3 parts of cetyltrimethylammonium bromide;

[0205] The quality indicators of the obtained high molecular weight methyl bromide epoxy resin are as follows:

[0206] The weight average molecular weight is 34200, the melting point is 146.6°C, the acid value is 1.20 mgkoh / g, the color is (10%, APHA) 50, and the bromine content is 51.83%.

[0207] Since the catalyst hexadecyltrimethylammonium bromide has a poor catalytic effect, the molecular weight, acid value and melting point of the obtained methyl bromide epoxy resin are unqualified.

[0208] Comparative Example 4

[0209] The preparation method of the low molecular weight methyl bromide epoxy resin and the high molecular weight methyl bromide epoxy resin is the same as that of Comparative Example 1, except that:

[0210] 255 parts of low molecular weight methyl bromide epoxy resin;

[0211] 208 parts of tetrabromobisphenol A;

[0212] 1.1 parts of composite organic catalyst;

[0213] The weight average molecular weight is 51,000, the melting point is 149.6° C., the acid value is 0.50 mgkoh / g, the color is (10%, APHA) 45, and the bromine content is 51.88%.

[0214] Since the amount of tetrabromobisphenol A was too much, the acid value of the obtained methyl bromide epoxy resin was unqualified.

[0215] Comparative Example 5

[0216] First, a low molecular weight brominated epoxy resin is prepared, comprising the following components in parts by weight:

[0217]

[0218] The preparation method of the low molecular weight methyl bromide epoxy resin comprises the following steps:

[0219] (1) putting methyl epichlorohydrin, tetrabromobisphenol A and crown ether catalyst into a reactor;

[0220] (2) heating under nitrogen protection and maintaining the ring-opening reaction at 108°C for 4 hours;

[0221] (3) Excess methyl epichlorohydrin was distilled under reduced pressure to 139°C, with a vacuum degree of -0.095 MPa and no effluent;

[0222] (4) Fill with nitrogen, cool to 90°C, add toluene, and stir for 20 minutes;

[0223] (5) adding 30% liquid caustic soda and carrying out the ring-closure reaction at 89°C for 6 hours;

[0224] (6) Wash with 89°C deionized water until neutral;

[0225] (7) heating and reducing the pressure to distill the obtained low molecular weight methyl bromide epoxy resin until the temperature reaches 134° C. and the vacuum degree reaches -0.095 MPa;

[0226] (8) The epoxy value of the low molecular weight methyl bromide epoxy resin was tested to be 0.280, and the resin was metered and transferred into a polymerization kettle to prepare a high molecular weight methyl bromide epoxy resin;

[0227] Second, a high molecular weight methyl bromide epoxy resin was prepared, comprising the following components in parts by weight:

[0228] 255 parts of low molecular weight methyl bromide epoxy resin;

[0229] 197 parts of tetrabromobisphenol A;

[0230] 1.2 parts of composite organic catalyst;

[0231] The mass ratio of the crown ether catalyst, benzyltriphenylphosphonium bromide and hexadecyltrimethylammonium bromide in the composite organic catalyst is 2:1:1.

[0232] The preparation method of high molecular weight methyl bromide epoxy resin comprises the following steps:

[0233] (1) adding low molecular weight methyl bromide epoxy resin, tetrabromobisphenol and composite organic catalyst into a reaction kettle;

[0234] (2) stirring and heating under nitrogen protection, and polymerizing at 208°C for 62 minutes;

[0235] (3) taking a sample to measure the acid value, and discharging the material when the acid value is 0.3 mgkoh / g to obtain a high molecular weight methyl bromide epoxy resin;

[0236] The quality indicators of the obtained high molecular weight methyl bromide epoxy resin are as follows:

[0237] The weight average molecular weight is 35700, the melting point is 149.3°C, the acid value is 0.60 mgkoh / g, the color is (10%, APHA) 55, and the bromine content is 51.80%.

[0238] Since the amount of methyl epichlorohydrin used in the production of low molecular weight methyl bromide epoxy resin is too small, the epoxy value of the low molecular weight methyl bromide epoxy resin is too low (0.280), which in turn causes the molecular weight, acid value and color of the obtained methyl bromide epoxy resin to be unqualified.

[0239] Comparative Example 6

[0240] First, a low molecular weight methyl bromide epoxy resin is prepared, comprising the following components in parts by weight:

[0241]

[0242] The preparation method of the low molecular weight methyl bromide epoxy resin comprises the following steps:

[0243] (1) putting methyl epichlorohydrin, tetrabromobisphenol A and crown ether catalyst into a reactor;

[0244] (2) heating under nitrogen protection and maintaining the ring-opening reaction at 108°C for 4 hours;

[0245] (3) Excess methyl epichlorohydrin was distilled under reduced pressure to 139°C, with a vacuum degree of -0.095 MPa and no effluent;

[0246] (4) Fill with nitrogen, cool to 90°C, add toluene, and stir for 20 minutes;

[0247] (5) adding 30% liquid caustic soda and carrying out the ring-closure reaction at 88°C for 6 hours;

[0248] (6) Wash with 87°C deionized water until neutral;

[0249] (7) heating and reducing the pressure to distill the obtained low molecular weight methyl bromide epoxy resin until the temperature reaches 135° C. and the vacuum degree reaches -0.095 MPa;

[0250] (8) The epoxy value of the low molecular weight methyl bromide epoxy resin was tested to be 0.283, and the resin was metered into a polymerization reactor to prepare a high molecular weight methyl bromide epoxy resin;

[0251] Second, a high molecular weight methyl bromide epoxy resin was prepared, comprising the following components in parts by weight:

[0252] 255 parts of low molecular weight methyl bromide epoxy resin;

[0253] 198 parts of tetrabromobisphenol A;

[0254] 1.2 parts of composite organic catalyst;

[0255] The mass ratio of the crown ether catalyst, benzyltriphenylphosphonium bromide and hexadecyltrimethylammonium bromide in the composite organic catalyst is 2:1:1.

[0256] The preparation method of the high molecular weight methyl bromide epoxy resin comprises the following steps:

[0257] (1) adding low molecular weight methyl bromide epoxy resin, tetrabromobisphenol A and composite organic catalyst into a reaction kettle;

[0258] (2) stirring and heating under nitrogen protection, and polymerizing at 208°C for 75 minutes;

[0259] (3) taking a sample to measure the acid value, and discharging the material when the acid value is 0.3 mgkoh / g to obtain a high molecular weight methyl bromide epoxy resin;

[0260] The quality indicators of the obtained high molecular weight methyl bromide epoxy resin are as follows:

[0261] The weight average molecular weight is 36900, the melting point is 149.7°C, the acid value is 0.50 mgkoh / g, the color is (10%, APHA) 52, and the bromine content is 51.83%.

[0262] Due to excessive use of methyl epichlorohydrin in the synthesis of low molecular weight methyl bromide epoxy resin, the removal process took 50 minutes longer than normal, causing the material obtained from the ring-opening reaction to reside at 139°C for a longer time, resulting in the epoxy value of the obtained low molecular weight methyl bromide epoxy resin being low, which further led to the molecular weight, acid value and color of the prepared high molecular weight methyl bromide epoxy resin being unqualified.

[0263] Application Example 1

[0264] 50 wt% of PBT resin, 50 wt% of PET resin, 10 wt% of ultra-high molecular weight methyl bromide epoxy resin of Example 1, 3.3 wt% of antimony trioxide and 2.5 wt% of toughening agent were mixed evenly and fed into a screw machine to obtain a flame retardant hair masterbatch; the flame retardant hair masterbatch was heated and extruded into a spinning machine to obtain flame retardant hair. The appearance of the obtained flame retardant hair is as follows: Figure 2 As shown, the brightness of flame-retardant hair is significantly improved, the flame-retardant effect reaches UL94-V0 level, and the physical and chemical properties are even better.

[0265] Comparative Application Example 1

[0266] 50 wt% of PBT resin, 50 wt% of PET resin, 13.5 wt% of FR-2400 high molecular weight brominated epoxy resin (produced by Israel Chemical Group, with a weight average molecular weight of 50,000) synthesized from epichlorohydrin and tetrabromobisphenol A, 4.5 wt% of antimony trioxide and 2.5 wt% of toughening agent were mixed evenly, and the mixture was fed into a screw machine to obtain a flame retardant hair masterbatch; the flame retardant hair masterbatch was heated and extruded into a spinning machine to obtain flame retardant hair. The appearance of the obtained flame retardant hair is as shown below. Figure 3 As shown, the brightness of the flame retardant hair is poor, the flame retardant effect only reaches UL94-V1 level, and the quality of the flame retardant hair is poor.

[0267] The molecular weight of the ultra-high molecular weight methyl bromide epoxy resin prepared in Example 1 of the present invention was tested by gel chromatography. The results are as follows: Figure 4 As shown in Table 1:

[0268] Table 1 Molecular weight of ultra-high molecular weight methyl bromide epoxy resin prepared in Example 1 of the present invention

[0269] project <![CDATA[Number average molecular weight M n > <![CDATA[Weight-average molecular weight M w > Gradient D Example 1 24553 50102 2.0406

[0270] As shown in Table 1, the ultra-high molecular weight methyl bromide epoxy resin prepared in Example 1 of the present invention has a number average molecular weight of 24553, a weight average molecular weight of 50102, and a gradient D (ratio of weight average molecular weight to number average molecular weight) of 2.0406. It can be seen that the ultra-high molecular weight methyl bromide epoxy resin provided by the present invention has a very high molecular weight.

[0271] according to Figure 4 It can be seen that the ultra-high molecular weight methyl bromide epoxy resin prepared in Example 1 of the present invention has a narrow molecular weight distribution. At the same time, since the ultra-high molecular weight methyl bromide epoxy resin contains more methyl side chains, it is conducive to blending with other resins, thereby improving the modification effect on other resins.

[0272] As can be seen from the above examples, the ultra-high molecular weight methyl bromide epoxy resin provided by the present invention has high molecular weight, narrow molecular weight distribution, good miscibility with other resins, better UV resistance and weather resistance, and is particularly suitable for flame-retardant hair modification.

[0273] Although the above embodiment provides a detailed description of the present invention, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the scope of protection of the present invention.

Claims

1. A method for preparing an ultra-high molecular weight methyl bromide epoxy resin, comprising the following steps: (1) Methyl epichlorohydrin, the first portion of tetrabromobisphenol A and a crown ether catalyst are mixed to perform a ring-opening reaction to obtain an intermediate product, brominated bisphenol A chlorohydrin ether, with the molecular formula C 23 H 26 Br4Cl2O4, the structural formula is shown in Formula I: (2) The intermediate product, toluene and liquid alkali are mixed to carry out a ring-closing reaction to obtain a low molecular weight methyl bromide epoxy resin with a molecular formula of C 23 H 24 Br4O4, molecular weight is 684, and the structural formula is shown in Formula II: (3) mixing the low molecular weight methyl bromide epoxy resin, a second portion of tetrabromobisphenol A and a composite organic catalyst to carry out a polymerization reaction to obtain an ultrahigh molecular weight methyl bromide epoxy resin; The molecular formula of the crown ether catalyst is C 20 H 24 O6, the structural formula is shown in Formula III: The composite organic catalyst is a crown ether catalyst and an organic catalyst; the organic catalyst is benzyltriphenylphosphine bromide and hexadecyltrimethylammonium bromide; the mass ratio of the crown ether catalyst, benzyltriphenylphosphine bromide and hexadecyltrimethylammonium bromide is 2:1:1; The mass ratio of the methyl epichlorohydrin to the first portion of tetrabromobisphenol A is 200-1000:500; The mass ratio of the methyl epichlorohydrin to the crown ether catalyst is 200-1000:1-4; The mass ratio of the low molecular weight methyl brominated epoxy resin to the second portion of tetrabromobisphenol A is 255:195-205.

2. The preparation method according to claim 1, characterized in that The mass ratio of methyl epichlorohydrin to toluene is 200-1000:400; The mass ratio of methyl epichlorohydrin to liquid caustic soda is 200-1000:250-450; The concentration of the liquid caustic soda is 28-32 wt%.

3. The preparation method according to claim 1, characterized in that The mass ratio of the low molecular weight methyl bromide epoxy resin to the composite organic catalyst is 255:0.8-1.

5.

4. The preparation method according to claim 1, characterized in that The ring-opening reaction temperature is 105-110° C., the holding time is 4-4.5 hours, and the ring-opening reaction is carried out under nitrogen protection; The temperature of the ring-closing reaction is 85-90° C., and the insulation time is 5.5-6.5 hours.

5. The preparation method according to claim 1, characterized in that The polymerization reaction temperature is 180-210° C., and the heat preservation time is 60-80 minutes; the polymerization reaction is carried out under nitrogen protection.

6. The ultra-high molecular weight methyl bromide epoxy resin obtained by the preparation method according to any one of claims 1 to 5, wherein the ultra-high molecular weight methyl bromide epoxy resin has a weight average molecular weight of 40,000 to 60,000, an epoxy value of 0.0033 to 0.005 eq / 100g, and a melting point of 147 to 153°C. The structural formula of the ultra-high molecular weight methyl bromide epoxy resin is shown in Formula IV: in, The value range of n is 32 to 48.

7. Use of the ultra-high molecular weight methyl bromide epoxy resin according to claim 6 in resin modification.

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