CN112898930A - Preparation method of flame-retardant duct piece adhesive - Google Patents
Preparation method of flame-retardant duct piece adhesive Download PDFInfo
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- CN112898930A CN112898930A CN202110235347.4A CN202110235347A CN112898930A CN 112898930 A CN112898930 A CN 112898930A CN 202110235347 A CN202110235347 A CN 202110235347A CN 112898930 A CN112898930 A CN 112898930A
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- flame
- epoxy resin
- retardant
- reaction
- pipe
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- 239000000853 adhesive Substances 0.000 title claims abstract description 80
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 80
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003063 flame retardant Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 122
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 122
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000010703 silicon Substances 0.000 claims abstract description 72
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 72
- 238000002156 mixing Methods 0.000 claims abstract description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- 239000011574 phosphorus Substances 0.000 claims abstract description 38
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 96
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
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- 239000002994 raw material Substances 0.000 claims description 28
- 239000003963 antioxidant agent Substances 0.000 claims description 26
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 238000009210 therapy by ultrasound Methods 0.000 claims description 20
- 239000011701 zinc Substances 0.000 claims description 20
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 230000000149 penetrating effect Effects 0.000 claims description 13
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 11
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 10
- 239000012990 dithiocarbamate Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- GVKDLCPTYCLSQW-YFKNTREVSA-N C(\C=C/C(=O)OC(C)CCCCCC)(=O)OC(C)CCCCCC.[Na] Chemical group C(\C=C/C(=O)OC(C)CCCCCC)(=O)OC(C)CCCCCC.[Na] GVKDLCPTYCLSQW-YFKNTREVSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000007974 melamines Chemical class 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 11
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003607 modifier Substances 0.000 abstract description 8
- 238000006757 chemical reactions by type Methods 0.000 abstract description 3
- 238000002715 modification method Methods 0.000 abstract description 3
- 230000002457 bidirectional effect Effects 0.000 abstract description 2
- 230000007812 deficiency Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- -1 accelerators Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a preparation method of a flame-retardant duct piece adhesive, which comprises the following steps of (1) preparing phosphorus flame-retardant epoxy resin; (2) preparing silicon flame-retardant epoxy resin; (3) and (4) synthesizing an adhesive. According to the invention, an adhesive mixing reaction type modification method is adopted, and the flame-retardant adhesive is obtained by modifying the phosphorus-containing flame-retardant modifier and the silicon-containing flame-retardant modifier together, so that the adhesive is endowed with an excellent flame-retardant effect, two epoxy resins make up for the deficiency to achieve a bidirectional flame-retardant effect, the two epoxy resins are fully mixed, the high viscosity of the epoxy resins is kept, and the problem of insufficient viscosity of the modified adhesive is avoided. In the step of synthesizing the adhesive, the two epoxy resins are mixed by an ultrasonic method to achieve the aim of uniform mixing, so that the phosphorus-containing groups and the silicon-containing groups are uniformly distributed, the flame-retardant coverage of the adhesive is wider, and the flame-retardant effect is more uniform.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a preparation method of a flame-retardant duct piece adhesive.
Background
The adhesive can be used for connecting same or two or more same or different workpieces (or materials) together, and after being cured, the organic or inorganic, natural or synthetic substances with sufficient strength are generally called adhesives or adhesives, bonding agents and are conventionally called as glue for short.
Conventional adhesives are classified into natural high molecular compounds (starch, animal skin glue, bone glue, natural rubber, etc.), synthetic high molecular compounds (thermosetting resins such as epoxy resin, phenol resin, urea resin, and polyurethane, thermoplastic resins such as polyvinyl acetal and perchloroethylene, and synthetic rubbers such as chloroprene rubber and nitrile rubber), and inorganic compounds (silicates, phosphates, etc.). Curing agents, accelerators, reinforcing agents, olefinic release agents, fillers, and the like are often incorporated into the adhesive depending on the application requirements. According to the classification of the application, warm glue, sealant, structural glue and the like can be separated. The adhesive is classified into room temperature curing adhesive, pressure sensitive adhesive and the like according to the using process. The application of the adhesive can connect the dissimilar materials and the sheet materials, and the stress distribution at the glued joint is uniform. Epoxy resin, neoprene, sealants and the like are commonly used in the manufacture and repair of containers. In recent years, organic adhesives have been widely used, and the adhesive bonding technology has been developed and become one of the three current technologies of adhesive bonding, welding and mechanical bonding.
The shield segment is a main assembly component for shield construction, is the innermost barrier of the tunnel and plays a role in resisting soil layer pressure, underground water pressure and some special loads. The shield segment is a permanent lining structure of a shield tunnel, and the quality of the shield segment is directly related to the overall quality and safety of the tunnel, so that the waterproof performance and the durability of the tunnel are influenced.
The duct piece adhesive needs to have strong bonding force due to application to shield construction, and in order to have strong bonding force, the flame retardant property of the duct piece adhesive is often ignored; in addition, the existing flame-retardant modification process of the adhesive has obvious defects, the molecular structure of the adhesive can be damaged to a certain extent, the adhesive force of the adhesive is damaged, and the flame-retardant effect is not ideal.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a flame-retardant duct piece adhesive, which adopts an adhesive mixing reaction type modification method, and obtains the flame-retardant adhesive by modifying the phosphorus-containing flame-retardant modifier and the silicon-containing flame-retardant modifier together, so that the adhesive is endowed with excellent flame-retardant effect, the phosphorus-containing flame-retardant modifier and the silicon-containing flame-retardant modifier are fully mixed, the high viscosity of epoxy resin is kept, and the problem of insufficient viscosity of the modified adhesive is avoided.
In order to solve the technical problems, the following technical scheme is adopted:
the preparation method of the flame-retardant duct piece adhesive is characterized by comprising the following steps of:
(1) preparing phosphorus flame-retardant epoxy resin: ultrasonic softening 60-80 parts of epoxy resin at 40-48 ℃ for 5-10min, and adding the epoxy resin into a reactor after ultrasonic treatment; adding 10-30 parts of phosphate melamine salt into a reactor, stirring and reacting at 100-120 ℃ for 60-90min to obtain phosphorus epoxy resin after reaction, and taking out for later use; the reaction is carried out under nitrogen atmosphere;
(2) preparing silicon flame-retardant epoxy resin: adding 40-60 parts of organic siloxane, 40-50 parts of absolute ethyl alcohol and a proper amount of distilled water into a reactor, starting stirring and refluxing, adjusting the pH value to 4.5-5, reacting at 65-70 ℃ for 2.5h, and separating after reaction to obtain organic silicon resin;
dissolving 50-65 parts of epoxy resin and the prepared organic silicon resin in an organic solvent, stirring to fully dissolve the epoxy resin and the prepared organic silicon resin, adding a catalyst, then starting heating to react, controlling the reaction temperature at 120-140 ℃ and the reaction time at 1.5-2h, and separating after the reaction is finished to obtain the organic silicon modified epoxy resin serving as the silicon epoxy resin for later use;
(3) synthesizing an adhesive: firstly, mixing phosphorus epoxy resin and silicon epoxy resin, and performing thermal ultrasonic treatment at 50-60 ℃ for 20-30 min; immediately adding the mixture into a mixing roll preheated to 60 ℃ after ultrasonic treatment, and adding 1-2 parts of antioxidant, 1-4 parts of tackifier, 1-4 parts of toughening agent, 1 part of accelerant and 0.5 part of penetrating agent into the mixing roll to mix for 30 min; and adding the antioxidant, the tackifier, the flexibilizer, the accelerant and the penetrating agent in the same parts, and mixing for 30min to prepare the flame-retardant duct piece adhesive.
Preferably, in the step (1), intermittent ultraviolet irradiation is provided during the reaction of the epoxy resin and the melamine phosphate; and starting the ultraviolet lamp every 5min and irradiating for 5 min. The ultraviolet lamp provides ultraviolet rays, and can activate raw material molecules to enable the raw material molecules to be in an active state, so that the reaction rate can be accelerated, and on the other hand, a plurality of phosphate melamine groups can be introduced to the epoxy resin as far as possible, and the flame retardant effect of the epoxy resin is improved.
Preferably, a crosslinking agent N, N-methylene bisacrylamide or divinylbenzene is added in the reaction process of the step (1) and the step (2). The modified epoxy resin molecules are converted into a three-dimensional network structure through the cross-linking agent, so that the strength, the heat resistance, the wear resistance and the performance are improved, and the practicability of the adhesive is higher.
Preferably, the phosphorus-based epoxy resin and the silicon-based epoxy resin are obtained by separating in the steps (1) and (2) in a reduced pressure distillation mode. The reduced pressure distillation operation is convenient, the obtained phosphorus-series epoxy resin and silicon-series epoxy resin have very high purity, and foreign matters are not doped in the adhesive, so that the high-efficiency viscosity, flame retardance, structural strength and the like can be maintained.
Preferably, the antioxidant is zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate, and the mass ratio of the zinc dialkyl dithiophosphate to the zinc dialkyl dithiocarbamate is 2:1 to compound the compound antioxidant. The antioxidant can delay or inhibit the polymer oxidation process, thereby preventing the aging of the polymer and prolonging the service life of the polymer, and the practicability is strong. .
Preferably, the adhesion promoter is a silicone adhesion promoter. The organic silicon tackifier not only can obviously increase the viscosity of the adhesive, but also has a certain flame retardant function, and further improves the flame retardant effect.
Preferably, the toughening agent is one or two of polyether, polysulfone, polyimide or hydroxy liquid butyronitrile. The adhesive has low elongation and high brittleness after being cured, and when the bonding part bears external force, cracks are easy to generate and rapidly spread to cause the cracking of a glue layer, so the adhesive is not fatigue-resistant and cannot be used for structural bonding. Therefore, the brittleness is reduced, the toughness is increased and the bearing strength of the adhesive is improved by adding the toughening agent.
Further, the accelerant is one of N, N-dimethylbenzyl, triethanolamine or polyether amine; the penetrating agent is sodium di-sec-octyl maleate sulfonate. The promoter helps to increase the reaction rate; the adhesive is conveniently used by a diluent.
Further, the reactor is a reaction-distillation integrated reaction device and comprises a reaction body, support legs and a distillation body, wherein the reaction body comprises a reaction cavity, a weighing feeder and a discharging pipe; a first heater is arranged in the reaction cavity, and the weighing feeder feeds materials to the reaction cavity after self-weighing; the distillation machine body comprises a distillation box, a condensation pipe, a condensation box and a discharge pipe; the lower end of the blanking pipe is connected to the distillation box, and the blanking pipe is provided with a first electromagnetic valve; the condenser pipe is connected between the distillation box and the condenser box, the discharge pipe is connected to the discharge port of the distillation box, the discharge pipe is connected with a second electromagnetic valve, a second heater is installed in the distillation box, and the pressure reducing valve is further installed in the distillation box to control air pressure in the distillation box. The invention designs a special reactor which consists of a reactor body, support legs and a distiller body, wherein the reactor body is used for the modification reaction of the step (1) and the step (2), a reaction product is directly conveyed to the distiller body through a blanking pipe after the reaction is finished, and the distiller body carries out reduced pressure distillation on the reaction product so as to obtain phosphorus flame-retardant epoxy resin and silicon flame-retardant epoxy resin; the reactor integrates the reaction and distillation functions, can directly complete the reaction and distillation processes in the reactor, avoids other artificial transfer steps, reduces the artificial loss of products, improves the collection rate of the products, and greatly accelerates the preparation speed.
In addition, the reactor body also comprises a weighing feeder, so that the purpose of quantitatively adding raw materials is achieved, other electronic scales are not needed, and the weighed raw materials directly enter the reaction cavity without loss. The first electromagnetic valve is used for controlling the opening and closing of the blanking pipe, and is convenient to control; the second electromagnetic valve is used for controlling the opening and closing of the discharge pipe, so that the control is convenient; the two condensation pipes are arranged, so that the condensation rate is higher.
Further, the weighing type feeder comprises an operation panel, a weighing device and a feeding pipe, the weighing device comprises a hopper, a weighing sensor and a feeding pipe, the weighing sensor supports and weighs the hopper, the feeding pipe is connected with an inner cavity of the hopper, the other end of the feeding pipe feeds materials to the feeding pipe, the feeding pipe is connected with a reaction cavity, and the feeding pipe is connected with a third electromagnetic valve; the operation panel comprises a setting key, a display screen and a built-in controller, the setting key is provided with weighing parameters, the display screen displays weighing data, the controller is connected with the weighing sensor and the electromagnetic valve III, and accurately metered raw materials are automatically added into the reaction cavity by controlling the electromagnetic valve III according to the set weighing parameters and the weight data detected by the weighing sensor; the reactor also comprises a washing tank, wherein the washing tank comprises a water inlet pipe and a water outlet pipe, washing water is fed into the water inlet pipe, and the water outlet pipe is connected with the reaction cavity; and the second electromagnetic valve is a three-way electromagnetic valve and is connected with a drain pipe, and the washing water is discharged through the drain pipe. This weighing type feeder can accomplish the process of weighing and throwing the material, and its principle is: at first, the adding weight of the current raw materials is set through a setting key, the adding weight is stored in a controller, a weighing sensor detects the weight of the current raw materials in a hopper in real time, a weight signal is transmitted to the controller, when the controller recognizes that the weight of the current raw materials reaches the adding weight, a third electromagnetic valve is opened, the raw materials are directly put into a reaction cavity, automatic raw material weighing and adding are achieved, and the automatic weighing and adding device has the advantages of convenience, rapidness and accuracy.
The washing box is used for providing washing water, and washing the reaction machine body and the distillation machine body through the washing water so as to achieve the purpose of convenient washing; the three-way electromagnetic valve is arranged to be connected with the drain pipe, so that the discharge of the waste water after washing is conveniently controlled.
Due to the adoption of the technical scheme, the method has the following beneficial effects:
the invention relates to a preparation method of a flame-retardant duct piece adhesive, aiming at the defects in the prior art, a mixed reaction type modification method of the adhesive is adopted, and the flame-retardant adhesive is obtained by modifying a phosphorus-containing flame-retardant modifier and a silicon-containing flame-retardant modifier together, so that the adhesive is endowed with an excellent flame-retardant effect, two epoxy resins make up for the deficiency to achieve a bidirectional flame-retardant effect, the two epoxy resins are fully mixed to keep the high viscosity of the epoxy resins, and the problem that the viscosity of the modified adhesive is insufficient is solved.
In the step of synthesizing the adhesive, the two epoxy resins are mixed by an ultrasonic method to achieve the aim of uniform mixing, so that the phosphorus-containing groups and the silicon-containing groups are uniformly distributed, the flame-retardant coverage of the adhesive is wider, and the flame-retardant effect is more uniform.
The ultraviolet lamp provides ultraviolet rays, and can activate raw material molecules to enable the raw material molecules to be in an active state, so that the reaction rate can be accelerated, and on the other hand, a plurality of phosphate melamine groups can be introduced to the epoxy resin as far as possible, and the flame retardant effect of the epoxy resin is improved.
The reduced pressure distillation operation is convenient, the obtained phosphorus-series epoxy resin and silicon-series epoxy resin have very high purity, and foreign matters are not doped in the adhesive, so that the high-efficiency viscosity, flame retardance, structural strength and the like can be maintained.
The invention designs a special reactor which consists of a reactor body, support legs and a distiller body, wherein the reactor body is used for the modification reaction of the step (1) and the step (2), a reaction product is directly conveyed to the distiller body through a blanking pipe after the reaction is finished, and the distiller body carries out reduced pressure distillation on the reaction product so as to obtain phosphorus flame-retardant epoxy resin and silicon flame-retardant epoxy resin; the reactor integrates the reaction and distillation functions, can directly complete the reaction and distillation processes in the reactor, avoids other artificial transfer steps, reduces the artificial loss of products, improves the collection rate of the products, and greatly accelerates the preparation speed.
In addition, the reactor body also comprises a weighing feeder, so that the purpose of quantitatively adding raw materials is achieved, other electronic scales are not needed, and the weighed raw materials directly enter the reaction cavity without loss. The first electromagnetic valve is used for controlling the opening and closing of the blanking pipe, and is convenient to control; the second electromagnetic valve is used for controlling the opening and closing of the discharge pipe, so that the control is convenient; the two condensation pipes are arranged, so that the condensation rate is higher.
This weighing type feeder can accomplish the process of weighing and throwing the material, and its principle is: at first, the adding weight of the current raw materials is set through a setting key, the adding weight is stored in a controller, a weighing sensor detects the weight of the current raw materials in a hopper in real time, a weight signal is transmitted to the controller, when the controller recognizes that the weight of the current raw materials reaches the adding weight, a third electromagnetic valve is opened, the raw materials are directly put into a reaction cavity, automatic raw material weighing and adding are achieved, and the automatic weighing and adding device has the advantages of convenience, rapidness and accuracy.
The washing box is used for providing washing water, and washing the reaction machine body and the distillation machine body through the washing water so as to achieve the purpose of convenient washing; the three-way electromagnetic valve is arranged to be connected with the drain pipe, so that the discharge of the waste water after washing is conveniently controlled.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic diagram of the structure of a reactor;
FIG. 2 is a schematic structural view of a distillation body;
FIG. 3 is a schematic structural diagram of a weighing feeder;
fig. 4 is a structural schematic diagram of a feeding pipe.
Detailed Description
As shown in fig. 1 to 4, a preparation method of a flame-retardant duct piece adhesive comprises the following steps:
(1) preparing phosphorus flame-retardant epoxy resin: ultrasonic softening 60-80 parts of epoxy resin at 40-48 ℃ for 5-10min, and adding the epoxy resin into a reactor after ultrasonic treatment; adding 10-30 parts of phosphate melamine salt into a reactor, stirring and reacting at 100-120 ℃ for 60-90min to obtain phosphorus epoxy resin after reaction, and taking out for later use; the reaction is carried out under nitrogen atmosphere;
(2) preparing silicon flame-retardant epoxy resin: adding 40-60 parts of organic siloxane, 40-50 parts of absolute ethyl alcohol and a proper amount of distilled water into a reactor, starting stirring and refluxing, adjusting the pH value to 4.5-5, reacting at 65-70 ℃ for 2.5h, and separating after reaction to obtain organic silicon resin;
dissolving 50-65 parts of epoxy resin and the prepared organic silicon resin in an organic solvent, stirring to fully dissolve the epoxy resin and the prepared organic silicon resin, adding nickel serving as a catalyst, starting heating to react, controlling the reaction temperature to be 120-140 ℃, reacting for 1.5-2h, and separating after the reaction is finished to obtain organic silicon modified epoxy resin serving as silicon epoxy resin for later use;
(3) synthesizing an adhesive: firstly, mixing phosphorus epoxy resin and silicon epoxy resin, and performing thermal ultrasonic treatment at 50-60 ℃ for 20-30 min; immediately adding the mixture into a mixing roll preheated to 60 ℃ after ultrasonic treatment, and adding 1-2 parts of antioxidant, 1-4 parts of tackifier, 1-4 parts of toughening agent, 1 part of accelerant and 0.5 part of penetrating agent into the mixing roll to mix for 30 min; and adding the antioxidant, the tackifier, the flexibilizer, the accelerant and the penetrating agent in the same parts, and mixing for 30min to prepare the flame-retardant duct piece adhesive.
In the step (1), intermittent ultraviolet irradiation is provided in the reaction process of the epoxy resin and the melamine salt of the phosphoric ester; and starting the ultraviolet lamp every 5min and irradiating for 5 min. The ultraviolet lamp provides ultraviolet rays, and can activate raw material molecules to enable the raw material molecules to be in an active state, so that the reaction rate can be accelerated, and on the other hand, a plurality of phosphate melamine groups can be introduced to the epoxy resin as far as possible, and the flame retardant effect of the epoxy resin is improved.
Adding a crosslinking agent N, N-methylene bisacrylamide or divinylbenzene in the reaction process of the step (1) and the step (2). The modified epoxy resin molecules are converted into a three-dimensional network structure through the cross-linking agent, so that the strength, the heat resistance, the wear resistance and the performance are improved, and the practicability of the adhesive is higher.
And (3) separating the phosphorus epoxy resin and the silicon epoxy resin in the steps (1) and (2) by adopting a reduced pressure distillation mode. The reduced pressure distillation operation is convenient, the obtained phosphorus-series epoxy resin and silicon-series epoxy resin have very high purity, and foreign matters are not doped in the adhesive, so that the high-efficiency viscosity, flame retardance, structural strength and the like can be maintained.
The antioxidant is zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate, and is prepared from the following components in a mass ratio of 2:1 to compound the compound antioxidant. The antioxidant can delay or inhibit the polymer oxidation process, thereby preventing the aging of the polymer and prolonging the service life of the polymer, and the practicability is strong. .
The tackifier is an organic silicon tackifier. The organic silicon tackifier not only can obviously increase the viscosity of the adhesive, but also has a certain flame retardant function, and further improves the flame retardant effect.
The toughening agent is one or two of polyether, polysulfone, polyimide or hydroxy liquid butyronitrile. The adhesive has low elongation and high brittleness after being cured, and when the bonding part bears external force, cracks are easy to generate and rapidly spread to cause the cracking of a glue layer, so the adhesive is not fatigue-resistant and cannot be used for structural bonding. Therefore, the brittleness is reduced, the toughness is increased and the bearing strength of the adhesive is improved by adding the toughening agent.
The accelerant is one of N, N-dimethylbenzyl, triethanolamine or polyether amine; the penetrating agent is sodium di-sec-octyl maleate sulfonate. The promoter helps to increase the reaction rate; the adhesive is conveniently used by a diluent.
The reactor is a reaction-distillation integrated reaction device and comprises a reactor body 1 at the upper part, support legs 2 and a distillation body 4 at the lower part, wherein the reactor body 1 comprises a reaction cavity 11, a weighing feeder 3 and a blanking pipe 13; a weighing feeder 3 is arranged at a feeding port of the reaction cavity 11, a feeding pipe 13 is connected with the feeding port of the reaction cavity 11, a first heater 12 is arranged in the reaction cavity 11, and the first heater 12 is a conventional heater and used for heating the reaction cavity 11; the weighing type feeder 3 has a weighing function, and feeds materials to the reaction cavity 11 after self-weighing; the distillation body 4 comprises a distillation box 41, a condensing pipe 43, a condensing box 44 and a discharging pipe 45; the lower end of the blanking pipe 13 is connected to the distillation box 41, the first electromagnetic valve 14 is installed on the blanking pipe 13, and the first electromagnetic valve 14 is a two-way electromagnetic valve; a condensing pipe 43 is connected between the distillation box 41 and the condensing box 44, two condensing pipes 43 are arranged, cold water is introduced into an interlayer of the condensing pipes 43 to achieve the condensation effect, the condensing box 44 is fixedly arranged on the reactor body 1, a discharge hole of the distillation box 41 is connected with a discharge pipe 45, the discharge pipe 45 is connected with a second electromagnetic valve 46, a second heater 42 is arranged in the distillation box 41, and the second heater 42 is a conventional heater and used for heating the inner cavity of the distillation box 41; the distillation box 41 is also provided with a conventional pressure reducing valve 48 for controlling the air pressure in the distillation box 41 to achieve the purpose of reduced pressure distillation. The invention designs a special reactor which is composed of a reactor body 1, support legs 2 and a distillation body 4, wherein the reactor body 1 is used for modification reaction in the steps (1) and (2), a reaction product is directly conveyed to the distillation body 4 through a feeding pipe 13 after the reaction is finished, and the distillation body 4 carries out reduced pressure distillation on the reaction product to obtain phosphorus flame-retardant epoxy resin and silicon flame-retardant epoxy resin; the reactor integrates the reaction and distillation functions, can directly complete the reaction and distillation processes in the reactor, avoids other artificial transfer steps, reduces the artificial loss of products, improves the collection rate of the products, and greatly accelerates the preparation speed.
In addition, the reactor body 1 also comprises a weighing feeder 3, so that the purpose of quantitatively adding raw materials is achieved, other electronic scales are not needed, and the weighed raw materials directly enter the reaction cavity 11 without loss. The first electromagnetic valve 14 is used for controlling the opening and closing of the blanking pipe 13, and is convenient to control; the second electromagnetic valve 46 is used for controlling the opening and closing of the discharge pipe 45, so that the control is convenient; the condensation pipes 43 are provided with two pipes, so that the condensation rate is higher.
The weighing type feeder 3 comprises an operation panel 32, a weighing device and a feeding pipe 36, the weighing device comprises a hopper 31, a weighing sensor 37 and a feeding pipe 311, the hopper 31 is used for feeding raw materials, the weighing sensor 37 supports and weighs the hopper 31, the feeding pipe 311 is connected with the inner cavity of the hopper 31, the other end of the feeding pipe 311 feeds the feeding pipe 36, the feeding pipe 36 is connected with the reaction cavity 11, the feeding pipe 311 is connected with a third electromagnetic valve 312, and the third electromagnetic valve 312 is a two-way electromagnetic valve and used for controlling the opening and closing of the feeding pipe 311; the operation panel 32 comprises a setting key 35, a display screen 33 and a built-in controller 34, wherein the setting key 35 is used for setting weighing parameters, the display screen 33 is used for displaying weighing data, the controller 34 is connected with a weighing sensor 37 and a third electromagnetic valve 312, and accurately metered raw materials are automatically added into the reaction cavity 11 by controlling the third electromagnetic valve 312 according to the set weighing parameters and the weight data detected by the weighing sensor 37; the reactor also comprises a washing tank 5, the washing tank 5 comprises a water inlet pipe 51 and a water outlet pipe 52, the water inlet pipe 51 sends washing water, and the water outlet pipe 52 is connected with the reaction cavity 11; the second solenoid valve 46 is a three-way solenoid valve, and is connected to a drain pipe 47, and the washing water is discharged through the drain pipe 47. This weighing type feeder 3 can accomplish the process of weighing and throwing the material, and its principle is: firstly, the adding weight of the current raw material is set through a setting key 35, the adding weight is stored in a controller 34, a weighing sensor 37 detects the weight of the current raw material added into a hopper 31 in real time, a weight signal is transmitted to the controller 34, when the controller 34 recognizes that the weight of the current raw material reaches the adding weight, a third electromagnetic valve 312 is opened, the raw material is directly added into a reaction cavity 11, automatic raw material weighing and adding are achieved, and the method has the advantages of convenience, rapidness and accuracy.
The washing box 5 is used for providing washing water, and washing the reaction machine body 1 and the distillation machine body 4 through the washing water so as to achieve the purpose of convenient washing; the drain pipe 47 is connected by arranging a three-way electromagnetic valve, so that the discharge of the waste water after washing is conveniently controlled.
In addition, a material feeding plate 38 is arranged at a port of the material feeding pipe 36, the material feeding plate 38 is of a partially through structure, and the weighing sensor 37 is arranged at the middle position of the material feeding plate 38, so that the purposes of weighing by the weighing sensor 37 and supporting the hopper 31 are achieved.
The invention is further illustrated by the following specific examples:
example 1
(1) Preparing phosphorus flame-retardant epoxy resin: 60 parts of epoxy resin is taken to be ultrasonically softened for 10min at the temperature of 45 ℃, added into a reactor after being ultrasonically treated, and nitrogen is introduced into the reactor; adding 10 parts of melamine phosphate and 1 part of N, N-methylene bisacrylamide serving as a cross-linking agent into a reactor, stirring and reacting for 60min at 100 ℃, providing intermittent ultraviolet irradiation in the reaction process, and starting an ultraviolet lamp every 5min and irradiating for 5 min; separating the obtained phosphorus epoxy resin by a reduced pressure distillation mode after the reaction is finished, and taking out the phosphorus epoxy resin for later use;
(2) preparing silicon flame-retardant epoxy resin: adding 40 parts of organic siloxane, 45 parts of absolute ethyl alcohol and a proper amount of distilled water into a reactor, starting stirring and refluxing, adjusting the pH value to 4.5-5, reacting at 65 ℃ for 2.5h, and separating after reaction to obtain organic silicon resin;
dissolving 52 parts of epoxy resin and the prepared organic silicon resin in an organic solvent, fully dissolving the epoxy resin and the prepared organic silicon resin by stirring, adding 1 part of cross-linking agent N, N-methylene bisacrylamide, starting heating reaction after taking nickel as a catalyst, controlling the reaction temperature at 120 ℃, reacting for 2 hours, and separating in a reduced pressure distillation mode after the reaction is finished to obtain the organic silicon modified epoxy resin serving as the silicon epoxy resin for later use;
(3) synthesizing an adhesive: firstly, mixing phosphorus epoxy resin and silicon epoxy resin, and performing thermal ultrasonic treatment at 50 ℃ for 20 min; immediately adding the mixture into a mixing mill preheated to 60 ℃ after ultrasonic treatment, and adding 2 parts of zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate into the mixing mill, mixing the mixture with 2:1 of a compounded antioxidant, 2 parts of an organic silicon tackifier, 2 parts of polyether, 1 part of N, N-dimethylbenzyl and 0.5 part of di-sec-octyl maleate sodium sulfonate, and mixing for 30 min; and adding the antioxidant, the tackifier, the flexibilizer, the accelerant and the penetrating agent in the same parts, and mixing for 30min to prepare the flame-retardant duct piece adhesive.
Example 2
(1) Preparing phosphorus flame-retardant epoxy resin: ultrasonically softening 70 epoxy resin at 45 ℃ for 10min, adding the epoxy resin into a reactor after ultrasonic treatment, and introducing nitrogen into the reactor; adding 15 parts of melamine salt of acid ester and 1 part of N, N-methylene bisacrylamide serving as a cross-linking agent into a reactor, stirring and reacting for 80min at 120 ℃, providing intermittent ultraviolet irradiation in the reaction process, and starting an ultraviolet lamp every 5min and irradiating for 5 min; separating the obtained phosphorus epoxy resin by a reduced pressure distillation mode after the reaction is finished, and taking out the phosphorus epoxy resin for later use;
(2) preparing silicon flame-retardant epoxy resin: adding 40 parts of organic siloxane, 50 parts of absolute ethyl alcohol and a proper amount of distilled water into a reactor, starting stirring and refluxing, adjusting the pH value to 4.5-5, reacting at 65 ℃ for 2.5h, and separating after reaction to obtain organic silicon resin;
dissolving 60 parts of epoxy resin and the prepared organic silicon resin in an organic solvent, fully dissolving the epoxy resin and the prepared organic silicon resin by stirring, adding 1 part of cross-linking agent N, N-methylene bisacrylamide, starting heating reaction after taking nickel as a catalyst, controlling the reaction temperature at 130 ℃, reacting for 2 hours, and separating in a reduced pressure distillation mode after the reaction is finished to obtain the organic silicon modified epoxy resin serving as the silicon epoxy resin for later use;
(3) synthesizing an adhesive: firstly, mixing phosphorus epoxy resin and silicon epoxy resin, and performing thermal ultrasonic treatment at 60 ℃ for 25 min; immediately adding the mixture into a mixing roll preheated to 60 ℃ after ultrasonic treatment, and adding 2 parts of zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate into the mixing roll, mixing the antioxidant, the organic silicon tackifier, the polyimide, the triethanolamine and the sodium di-sec-octyl maleate sulfonate into the mixing roll in a ratio of 2:1 for 30min, wherein the antioxidant is a composite antioxidant prepared by compounding 2 parts of zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate, 3 parts of organic silicon tackifier, 3 parts of polyimide, 1 part of triethanolamine and 0.5 part of sodium di-sec-; and adding the antioxidant, the tackifier, the flexibilizer, the accelerant and the penetrating agent in the same parts, and mixing for 30min to prepare the flame-retardant duct piece adhesive.
Example 3
(1) Preparing phosphorus flame-retardant epoxy resin: ultrasonically softening 70 oxygen resin at 48 ℃ for 10min, adding the resin into a reactor after ultrasonic treatment, and introducing nitrogen into the reactor; adding 20 parts of melamine salt of acid ester and 1 part of N, N-methylene bisacrylamide serving as a cross-linking agent into a reactor, stirring and reacting for 80min at 120 ℃, providing intermittent ultraviolet irradiation in the reaction process, and starting an ultraviolet lamp every 5min and irradiating for 5 min; separating the obtained phosphorus epoxy resin by a reduced pressure distillation mode after the reaction is finished, and taking out the phosphorus epoxy resin for later use;
(2) preparing silicon flame-retardant epoxy resin: adding 50 parts of organic siloxane, 50 parts of absolute ethyl alcohol and a proper amount of distilled water into a reactor, starting stirring and refluxing, adjusting the pH value to 4.5-5, reacting at 70 ℃ for 2.5h, and separating after reaction to obtain organic silicon resin;
dissolving 55 parts of epoxy resin and the prepared organic silicon resin in an organic solvent, fully dissolving the epoxy resin and the prepared organic silicon resin by stirring, adding 1 part of cross-linking agent N, N-methylene bisacrylamide, starting heating reaction after taking nickel as a catalyst, controlling the reaction temperature at 135 ℃, and the reaction time to be 1.8h, and after the reaction is finished, separating the epoxy resin in a reduced pressure distillation mode to obtain the organic silicon modified epoxy resin serving as silicon epoxy resin for later use;
(3) synthesizing an adhesive: firstly, mixing phosphorus epoxy resin and silicon epoxy resin, and performing thermal ultrasonic treatment at 60 ℃ for 25 min; immediately adding the mixture into a mixing roll preheated to 60 ℃ after ultrasonic treatment, and adding 2 parts of zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate into the mixing roll, mixing the antioxidant, the organic silicon tackifier, the polyimide, the triethanolamine and the sodium di-sec-octyl maleate sulfonate into the mixing roll in a ratio of 2:1 for 30min, wherein the antioxidant is a composite antioxidant prepared by compounding 2 parts of zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate, 3 parts of organic silicon tackifier, 3 parts of polyimide, 1 part of triethanolamine and 0.5 part of sodium di-sec-; and adding the antioxidant, the tackifier, the flexibilizer, the accelerant and the penetrating agent in the same parts, and mixing for 30min to prepare the flame-retardant duct piece adhesive.
Example 4
(1) Preparing phosphorus flame-retardant epoxy resin: ultrasonically softening 80 parts of epoxy resin at 45 ℃ for 10min, adding the epoxy resin into a reactor after ultrasonic treatment, and introducing nitrogen into the reactor; adding 30 parts of phosphate melamine salt and 1 part of cross-linking agent N, N-methylene bisacrylamide into a reactor, stirring and reacting for 90min at 120 ℃, providing intermittent ultraviolet irradiation in the reaction process, starting an ultraviolet lamp every 5min and irradiating for 5 min; separating the obtained phosphorus epoxy resin by a reduced pressure distillation mode after the reaction is finished, and taking out the phosphorus epoxy resin for later use;
(2) preparing silicon flame-retardant epoxy resin: adding 60 parts of organic siloxane, 50 parts of absolute ethyl alcohol and a proper amount of distilled water into a reactor, starting stirring and refluxing, adjusting the pH value to 4.5-5, reacting at 70 ℃ for 2.5h, and separating after reaction to obtain organic silicon resin;
dissolving 65 parts of epoxy resin and the prepared organic silicon resin in an organic solvent, fully dissolving the epoxy resin and the prepared organic silicon resin by stirring, adding 1 part of cross-linking agent N, N-methylene bisacrylamide, starting heating reaction after taking nickel as a catalyst, controlling the reaction temperature at 140 ℃, and the reaction time to be 2 hours, and after the reaction is finished, separating the epoxy resin in a reduced pressure distillation mode to obtain the organic silicon modified epoxy resin serving as the silicon epoxy resin for later use;
(3) synthesizing an adhesive: firstly, mixing phosphorus epoxy resin and silicon epoxy resin, and performing thermal ultrasonic treatment at 60 ℃ for 30 min; immediately adding the mixture into a mixing mill preheated to 60 ℃ after ultrasonic treatment, and adding 2 parts of zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate into the mixing mill, mixing the mixture with 2:1 of a composite antioxidant, 4 parts of an organic silicon tackifier, 4 parts of polysulfone, 1 part of polyether amine and 0.5 part of di-sec-octyl maleate sodium sulfonate, and mixing for 30 min; and adding the antioxidant, the tackifier, the flexibilizer, the accelerant and the penetrating agent in the same parts, and mixing for 30min to prepare the flame-retardant duct piece adhesive.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the same technical problems and achieve the same technical effects are all covered in the protection scope of the present invention.
Claims (10)
1. The preparation method of the flame-retardant duct piece adhesive is characterized by comprising the following steps of:
(1) preparing phosphorus flame-retardant epoxy resin: ultrasonic softening 60-80 parts of epoxy resin at 40-48 ℃ for 5-10min, and adding the epoxy resin into a reactor after ultrasonic treatment; adding 10-30 parts of phosphate melamine salt into a reactor, stirring and reacting at 100-120 ℃ for 60-90min to obtain phosphorus epoxy resin after reaction, and taking out for later use; the reaction is carried out under nitrogen atmosphere;
(2) preparing silicon flame-retardant epoxy resin: adding 40-60 parts of organic siloxane, 40-50 parts of absolute ethyl alcohol and a proper amount of distilled water into a reactor, starting stirring and refluxing, adjusting the pH value to 4.5-5, reacting at 65-70 ℃ for 2.5h, and separating after reaction to obtain organic silicon resin;
dissolving 50-65 parts of epoxy resin and the prepared organic silicon resin in an organic solvent, stirring to fully dissolve the epoxy resin and the prepared organic silicon resin, adding a catalyst, then starting heating to react, controlling the reaction temperature at 120-140 ℃ and the reaction time at 1.5-2h, and separating after the reaction is finished to obtain the organic silicon modified epoxy resin serving as the silicon epoxy resin for later use;
(3) synthesizing an adhesive: firstly, mixing phosphorus epoxy resin and silicon epoxy resin, and performing thermal ultrasonic treatment at 50-60 ℃ for 20-30 min; immediately adding the mixture into a mixing roll preheated to 60 ℃ after ultrasonic treatment, and adding 1-2 parts of antioxidant, 1-4 parts of tackifier, 1-4 parts of toughening agent, 1 part of accelerant and 0.5 part of penetrating agent into the mixing roll to mix for 30 min; and adding the antioxidant, the tackifier, the flexibilizer, the accelerant and the penetrating agent in the same parts, and mixing for 30min to prepare the flame-retardant duct piece adhesive.
2. The preparation method of the flame-retardant segment adhesive according to claim 1, which is characterized by comprising the following steps: in the step (1), intermittent ultraviolet irradiation is provided in the reaction process of the epoxy resin and the melamine salt of the phosphoric ester; and starting the ultraviolet lamp every 5min and irradiating for 5 min.
3. The preparation method of the flame-retardant segment adhesive according to claim 1, which is characterized by comprising the following steps: adding a crosslinking agent N, N-methylene bisacrylamide or divinylbenzene in the reaction process of the step (1) and the step (2).
4. The preparation method of the flame-retardant segment adhesive according to claim 1, which is characterized by comprising the following steps: and (3) separating the phosphorus epoxy resin and the silicon epoxy resin in the steps (1) and (2) by adopting a reduced pressure distillation mode.
5. The preparation method of the flame-retardant segment adhesive according to claim 1, which is characterized by comprising the following steps: the antioxidant is zinc dialkyl dithiophosphate and zinc dialkyl dithiocarbamate, and is prepared from the following components in a mass ratio of 2:1 to compound the compound antioxidant.
6. The preparation method of the flame-retardant segment adhesive according to claim 1, which is characterized by comprising the following steps: the tackifier is an organic silicon tackifier.
7. The preparation method of the flame-retardant segment adhesive according to claim 1, which is characterized by comprising the following steps: the toughening agent is one or two of polyether, polysulfone, polyimide or hydroxy liquid butyronitrile.
8. The preparation method of the flame-retardant segment adhesive according to claim 1, which is characterized by comprising the following steps: the accelerant is one of N, N-dimethylbenzyl, triethanolamine or polyether amine; the penetrating agent is sodium di-sec-octyl maleate sulfonate.
9. The preparation method of the flame-retardant segment adhesive according to claim 1, which is characterized by comprising the following steps: the reactor is a reaction-distillation integrated reaction device and comprises a reaction body, support legs and a distillation body, wherein the reaction body comprises a reaction cavity, a weighing type feeder and a discharging pipe; a first heater is arranged in the reaction cavity, and the weighing feeder feeds materials to the reaction cavity after self-weighing; the distillation machine body comprises a distillation box, a condenser pipe, a condenser box and a discharge pipe; the lower end of the blanking pipe is connected to the distillation box, and the blanking pipe is provided with a first electromagnetic valve; the condenser pipe is connected between the distillation box and the condenser box, the discharge pipe is connected to the discharge port of the distillation box, the discharge pipe is connected with a second electromagnetic valve, a second heater is installed in the distillation box, and the pressure reducing valve is further installed in the distillation box to control air pressure in the distillation box.
10. The preparation method of the flame-retardant segment adhesive according to claim 9, wherein the preparation method comprises the following steps: the weighing type feeder comprises an operation panel, a weighing device and a feeding pipe, the weighing device comprises a hopper, a weighing sensor and a feeding pipe, the weighing sensor supports and weighs the hopper, the feeding pipe is connected with an inner cavity of the hopper, the other end of the feeding pipe feeds materials to the feeding pipe, the feeding pipe is connected with a third electromagnetic valve, and the feeding pipe is connected with a reaction cavity; the operation panel comprises a setting key, a display screen and a built-in controller, the setting key is used for setting weighing parameters, the display screen is used for displaying weighing data, the controller is connected with the weighing sensor and the electromagnetic valve III, and accurately metered raw materials are automatically added into the reaction cavity by controlling the electromagnetic valve III according to the set weighing parameters and the weight data detected by the weighing sensor; the reactor also comprises a washing tank, the washing tank comprises a water inlet pipe and a water outlet pipe, the water inlet pipe is used for feeding washing water, and the water outlet pipe is connected with the reaction cavity; and the second electromagnetic valve is a three-way electromagnetic valve and is connected with a drain pipe, and the washing water is discharged through the drain pipe.
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