CN1234796C - Epoxy modified organic silicon resin adhesive - Google Patents
Epoxy modified organic silicon resin adhesive Download PDFInfo
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- CN1234796C CN1234796C CN 03133623 CN03133623A CN1234796C CN 1234796 C CN1234796 C CN 1234796C CN 03133623 CN03133623 CN 03133623 CN 03133623 A CN03133623 A CN 03133623A CN 1234796 C CN1234796 C CN 1234796C
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- modified silicone
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Abstract
The present invention relates to an epoxy modified organic silicone resin adhesive which is composed of 15 to 40 parts of epoxy modified organic silicone resin, 15 to 35 parts of epoxy resin, 10 to 25 parts of versamid, 10 to 25 parts of fillers, 2 to 8 parts of an amine solidifying agent and 2 to 8 parts of a coupling agent. The epoxy modified organic silicone resin in the epoxy modified organic silicone resin adhesive of the present invention is prepared mainly by a grafting method or a block copolymerization method, and thus, the present invention has both the characteristics of epoxy resin such as good adhesive property, high mechanical strength and shearing strength and good processability and the characteristics of the organic silicone resin such as high heat resistance and good elasticity. In addition, the present invention can be solidified at room temperature, and has the capacities of short-term use below 300 DEG C and long-term use below 200 DEG C.
Description
Technical field:
The present invention relates to resin adhesive, a kind of epoxy modified silicone resin tackiness agent that at high temperature uses that at room temperature solidifies is provided especially.
Background technology:
In some cases, need stick with glue agent usually and clog gap on the mechanical component, to guarantee the various connections sealings of machinery.More existing tackiness agent comprise: epoxy-butyronitrile, polyimide, spot welding glue, poly-ethanol acetal, rubber adhesive and organic silicon adhesive, and they have intermediate temperature setting or hot setting respectively, and comparatively high temps uses down; Perhaps solidify under room temperature or the middle temperature, the characteristics of using below 150 ℃, thus limited their use range.
Technology contents:
The object of the present invention is to provide a kind of epoxy modified silicone resin tackiness agent, it can be implemented under the room temperature and solidifies, and at high temperature uses, thereby has more extensive applicability.
The invention provides a kind of epoxy modified silicone resin tackiness agent, it is characterized in that consisting of, weight percent (among the present invention, except that specializing, being part by weight):
Epoxy modified silicone resin 15～40
Resins, epoxy 15～35
Versamid 10～25
Amine curing agent 2～8
Filler 10～25
Coupling agent 2～8
Wherein,
The epoxy group content of epoxy modified silicone resin requires at 0.06mol/L～0.08mol/L, and silicone content requires 8%～10%;
The oxirane value of Resins, epoxy requires at 0.4eq/100g～0.5eq/100g, and volatile content is not more than 1.0%;
The amine value of Versamid is in the scope of 200 ± 20mgKOH/g, and viscosity is 1 * 10
3～1 * 10
4MPaS;
Amine curing agent is selected from a kind of of diethylenetriamine, mphenylenediamine, diaminodiphenylmethane, hexahydropyridine;
Filler is selected from one or more of asbestos powder, titanium dioxide, lime carbonate, talcum powder;
Coupling agent is selected from a kind of of γ-An Jibingjisanyiyangjiguiwan KH-550, γ-epoxidation propoxy-propyl-triethoxysilicane KH560, anilinomethyl triethoxysilane Nanjing University-42.
The present invention also provides the preparation method of above-mentioned epoxy modified silicone resin tackiness agent, it is characterized in that:
---epoxy modified silicone resin is handled 50～60min down at 70～90 ℃;
---Resins, epoxy is added in the epoxy modified silicone resin of above-mentioned processing, the stirred in water bath that is placed on 50～60 ℃ is to mixing;
---Versamid and filler are added be stirred in the mixture of above-mentioned Resins, epoxy and epoxy modified silicone resin and mix;
---amine curing agent and coupling agent are added be stirred in the mixture of above-mentioned Resins, epoxy with Versamid and filler and epoxy modified silicone resin and mix, must finished product.
Among the preparation method of epoxy modified silicone resin tackiness agent of the present invention, when using titanium dioxide to make filler, should be at first with the temperature lower calcination 2～6h of titanium dioxide at 450～550 ℃.
In the epoxy modified silicone resin tackiness agent of the present invention, epoxy modified silicone resin is a material of main part, and it is to the character decisive role of tackiness agent.Usually, silicone resin has good thermotolerance, but needs 150～200 ℃ hot setting, and set time is long, and material adhesive power is low, organic solvent resistance is poor to being glued.The thermotolerance of Resins, epoxy is then relatively poor, but can utilize solidifying agent to realize self-vulcanizing, simultaneously to being glued material adhesive power height.If low-molecular-weight silicone resin and Resins, epoxy are carried out polycondensation, silanol groups in the silicone resin can form epoxide modified silicone resin with the effects such as hydroxyl, methylol and phenolic hydroxyl group in the Resins, epoxy, this epoxide modified silicone resin can keep the good thermostability of silicone resin, can utilize curing agent for epoxy resin to carry out self-vulcanizing again.This just requires the silicone content in the selected epoxy modified silicone resin to want suitably, and oxirane value is big as much as possible simultaneously.
Because the commercially available oxirane value that satisfies the epoxy modified silicone resin that certain silicone content requires is lower,, select for use to add Resins, epoxy as properties-correcting agent for the performance of the self-vulcanizing that further improves epoxy modified silicone resin tackiness agent of the present invention.
In the epoxy modified silicone resin tackiness agent of the present invention, Versamid can react with epoxy group(ing), and main effect is a solidifying agent, also has the effect of toughner simultaneously.
In the epoxy modified silicone resin tackiness agent of the present invention, amine curing agent adds for the hot strength that improves tackiness agent.
In the epoxy modified silicone resin tackiness agent of the present invention, used filler can also reduce the convergent force and the thermal stresses of glue-line except that the bonding strength that can increase tackiness agent with reducing cost, and especially can significantly improve the slip resistance under the high temperature.But the consumption of filler must be suitably, otherwise the mechanical modulus of glue-line is increased, and cementitious internal stress is increased and influences bonding quality.
In the epoxy modified silicone resin tackiness agent of the present invention, the use of coupling agent can improve the combining form at tackiness agent and adherend interface, makes surface physics absorption be converted into chemisorption, to improve the bonding strength and the ageing-resistant performance of glue-line.
In a word, epoxy modified silicone resin method in the epoxy modified silicone resin tackiness agent of the present invention obtains,, physical strength good with adhering with epoxy resin, slip resistance height and the good characteristics of workability have the characteristics of the high and good springiness of heat resistance of organic silicon resin simultaneously again.Can at room temperature solidify, have 300 ℃ of following short-terms and use, in the ability of 200 ℃ of following life-time service.
Embodiment:
Embodiment 1
As raw material, the outward appearance of epoxy modified silicone resin becomes the deep yellow thick liquid with commercially available epoxy modified silicone resin, Resins, epoxy, Versamid, and the content of epoxy group(ing) is 0.06mol/L, and the content of silicon is 10%.The oxirane value of Resins, epoxy is 0.5eq/100g, and volatile content is not more than 1.0%; The amine value of Versamid is in the scope of 200 ± 20mgKOH/g, and viscosity is 1 * 10
3MPaS; Amine curing agent is chosen as mphenylenediamine; Coupling agent is chosen as KH-550; With calcining 4h material in the High Temperature Furnaces Heating Apparatus of commercially available titanium dioxide powder under 500 ℃ of temperature.
Take by weighing the 15g epoxy modified silicone resin with balance in beaker, processing reaches certain viscosity under 80 ℃; The Resins, epoxy that adds 15g is put into 50～60 ℃ water-bath, and it is even carefully to be stirred to two kinds of mixed with resin; Add the Versamid of 10g and the titanium dioxide powder of 10g again, the mixing of materials that carefully is stirred in the beaker is even; Add the mphenylenediamine of 2g and the KH-550 of 2g again, carefully be stirred to and mix, the epoxy modified silicone resin tackiness agent.Its pull strength at room temperature is 23.6MPa, and the pull strength under 300 ℃ is 0.14MPa.
Embodiment 2
As raw material, the outward appearance of epoxy modified silicone resin becomes the deep yellow thick liquid with commercially available epoxy modified silicone resin, Resins, epoxy, Versamid, and the content of epoxy group(ing) is 0.06mol/L, and the content of silicon is 10%.The oxirane value of Resins, epoxy is 0.5eq/100g, and volatile content is not more than 1.0%; The amine value of Versamid is in the scope of 200 ± 20mgKOH/g, and viscosity is 1 * 10
3MPaS; Amine curing agent is chosen as mphenylenediamine; Coupling agent is chosen as KH-550; To calcine 4 hours in the High Temperature Furnaces Heating Apparatus of commercially available titanium dioxide powder under 500 ℃ of temperature as filler.
Take by weighing the 30g epoxy modified silicone resin with balance in beaker, processing reaches certain viscosity under 80 ℃; The Resins, epoxy that adds 30g is put into 50～60 ℃ water-bath, and it is even carefully to be stirred to two kinds of mixed with resin; Add the Versamid of 20g and the titanium dioxide powder of 20g again, the mixing of materials that carefully is stirred in the beaker is even; Add the mphenylenediamine of 6g and the KH-550 of 6g again, carefully be stirred to and mix, the epoxy modified silicone resin tackiness agent.Its pull strength at room temperature is 22.1MPa, and the pull strength under 200 ℃ is 0.41MPa, and the pull strength under 300 ℃ is 0.24MPa.
Embodiment 3
As raw material, the outward appearance of epoxy modified silicone resin becomes the deep yellow thick liquid with commercially available epoxy modified silicone resin, Resins, epoxy, Versamid, and the content of epoxy group(ing) is 0.06mol/L, and the content of silicon is 10%.The oxirane value of Resins, epoxy is 0.5eq/100g, and volatile content is not more than 1.0%; The amine value of Versamid is in the scope of 200 ± 20mgKOH/g, and viscosity is 1 * 10
3MPaS; Amine curing agent is chosen as diaminodiphenylmethane; Coupling agent is chosen as KH-550; With commercially available asbestos powder as filler.
Take by weighing the 40g epoxy modified silicone resin with balance in beaker, processing reaches certain viscosity under 80 ℃; The Resins, epoxy that adds 40g is put into 50～60 ℃ water-bath, and it is even carefully to be stirred to two kinds of mixed with resin; Add the Versamid of 25g and the asbestos powder of 25g again, the mixing of materials that carefully is stirred in the beaker is even; Add the diaminodiphenylmethane of 8g and the KH-550 of 8g again, carefully be stirred to and mix, the epoxy modified silicone resin tackiness agent.Its pull strength at room temperature is 21MPa, and the pull strength under 200 ℃ is 0.41MPa, and the pull strength under 300 ℃ is 0.13MPa.
Embodiment 4
As raw material, the outward appearance of epoxy modified silicone resin becomes the deep yellow thick liquid with commercially available epoxy modified silicone resin, Resins, epoxy, Versamid, and the content of epoxy group(ing) is 0.06mol/L, and the content of silicon is 10%.The oxirane value of Resins, epoxy is 0.5eq/100g, and volatile content is not more than 1.0%; The amine value of Versamid is in the scope of 200 ± 20mgKOH/g, and viscosity is 1 * 10
3MPaS; Amine curing agent is chosen as diaminodiphenylmethane; Coupling agent is chosen as KH-550; With commercially available asbestos powder as filler.
Take by weighing the 40g epoxy modified silicone resin with balance in beaker, processing reaches certain viscosity under 80 ℃; The Resins, epoxy that adds 25g is put into 50～60 ℃ water-bath, and it is even carefully to be stirred to two kinds of mixed with resin; Add the Versamid of 15g and the asbestos powder of 25g again, the mixing of materials that carefully is stirred in the beaker is even; Add the diaminodiphenylmethane of 6g and the KH-550 of 6g again, carefully be stirred to and mix, the epoxy modified silicone resin tackiness agent.Its pull strength at room temperature is 23.1MPa, and the pull strength under 200 ℃ is 0.39MPa, and the pull strength under 300 ℃ is 0.24MPa.
Embodiment 5
As raw material, the outward appearance of epoxy modified silicone resin becomes the deep yellow thick liquid with commercially available epoxy modified silicone resin, Resins, epoxy, Versamid, and the content of epoxy group(ing) is 0.06mol/L, and the content of silicon is 10%.The oxirane value of Resins, epoxy is 0.5eq/100g, and volatile content is not more than 1.0%; The amine value of Versamid is in the scope of 200 ± 20mgKOH/g, and viscosity is 1 * 10
3MPaS; Amine curing agent is chosen as hexahydropyridine; Coupling agent is chosen as KH-560; With commercially available talcum powder as filler.
Take by weighing the 40g epoxy modified silicone resin with balance in beaker, processing reaches certain viscosity under 80 ℃; The Resins, epoxy that adds 30g is put into 50～60 ℃ water-bath, and it is even carefully to be stirred to two kinds of mixed with resin; Add the Versamid of 20g and the talcum powder of 20g again, the mixing of materials that carefully is stirred in the beaker is even; Add the hexahydropyridine of 4g and the KH-560 of 4g again, carefully be stirred to and mix, the epoxy modified silicone resin tackiness agent.Its pull strength at room temperature is 24.1MPa, and the pull strength under 200 ℃ is 0.39MPa, and the pull strength under 300 ℃ is 0.10MPa.
Embodiment 6
As raw material, the outward appearance of epoxy modified silicone resin becomes the deep yellow thick liquid with commercially available epoxy modified silicone resin, Resins, epoxy, Versamid, and the content of epoxy group(ing) is 0.06mol/L, and the content of silicon is 10%.The oxirane value of Resins, epoxy is 0.5eq/100g, and volatile content is not more than 1.0%; The amine value of Versamid is in the scope of 200 ± 20mgKOH/g, and viscosity is 1 * 10
3MPaS; Amine curing agent is chosen as hexahydropyridine; Coupling agent is chosen as KH-560; With commercially available talcum powder as filler.
Take by weighing the 20g epoxy modified silicone resin with balance in beaker, processing reaches certain viscosity under 80 ℃; The Resins, epoxy that adds 15g is put into 50～60 ℃ water-bath, and it is even carefully to be stirred to two kinds of mixed with resin; Add the Versamid of 15g and the talcum powder of 15g again, the mixing of materials that carefully is stirred in the beaker is even; Add the hexahydropyridine of 2g and the KH-560 of 2g again, carefully be stirred to and mix, the epoxy modified silicone resin tackiness agent.Its pull strength at room temperature is 22.1MPa, and the pull strength under 200 ℃ is 0.28MPa, and the pull strength under 300 ℃ is 0.08MPa.
Claims (3)
1, a kind of epoxy modified silicone resin tackiness agent is characterized in that consisting of weight percent:
Epoxy modified silicone resin 15～40
Resins, epoxy 15～35
Versamid 10～25
Filler 10～25
Amine curing agent 2～8
Coupling agent 2～8
Wherein,
The epoxy group content of epoxy modified silicone resin requires at 0.06mol/L～0.08mol/L, and silicone content requires 8%～10%;
The oxirane value of Resins, epoxy requires at 0.4eq/100g～0.5eq/100g, and volatile content is not more than 1.0%;
The amine value of Versamid is in the scope of 200 ± 20mgKOH/g, and viscosity is 1 * 10
3～1 * 10
4MPaS;
Amine curing agent is selected from a kind of of diethylenetriamine, mphenylenediamine, diaminodiphenylmethane, hexahydropyridine;
Filler is selected from one or more of asbestos powder, titanium dioxide, lime carbonate, talcum powder;
Coupling agent is selected from a kind of of γ-An Jibingjisanyiyangjiguiwan, γ-epoxidation propoxy-propyl-triethoxysilicane, anilinomethyl triethoxysilane.
2, the preparation method of the described epoxy modified silicone resin tackiness agent of a kind of claim 1 is characterized in that:
---epoxy modified silicone resin is handled 50～60min down at 70～90 ℃;
---Resins, epoxy is added in the epoxy modified silicone resin of above-mentioned processing, the stirred in water bath that is placed on 50～60 ℃ is to mixing;
---Versamid and filler are added be stirred in the mixture of above-mentioned Resins, epoxy and epoxy modified silicone resin and mix;
---amine curing agent and coupling agent are added be stirred in the mixture of above-mentioned Resins, epoxy with Versamid and filler and epoxy modified silicone resin and mix, must finished product.
3, according to the preparation method of the described epoxy modified silicone resin tackiness agent of claim 2, it is characterized in that: when using titanium dioxide to make filler, the temperature lower calcination 2～6h of titanium dioxide at 450～550 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133623 CN1234796C (en) | 2003-08-01 | 2003-08-01 | Epoxy modified organic silicon resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133623 CN1234796C (en) | 2003-08-01 | 2003-08-01 | Epoxy modified organic silicon resin adhesive |
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|---|---|
| CN1580172A CN1580172A (en) | 2005-02-16 |
| CN1234796C true CN1234796C (en) | 2006-01-04 |
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|---|---|---|---|
| CN 03133623 Expired - Fee Related CN1234796C (en) | 2003-08-01 | 2003-08-01 | Epoxy modified organic silicon resin adhesive |
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| CN111171779A (en) * | 2018-11-11 | 2020-05-19 | 天津大学青岛海洋技术研究院 | Preparation method of wide-temperature-range high-temperature-resistant composite adhesive |
| CN112876850A (en) * | 2021-01-19 | 2021-06-01 | 苏州海特自动化设备有限公司 | High-heat-conductivity composition and heat-conducting film |
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