CN104448428A - Low VOC content expansion vibration-reduction rubber - Google Patents
Low VOC content expansion vibration-reduction rubber Download PDFInfo
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- CN104448428A CN104448428A CN201310421957.9A CN201310421957A CN104448428A CN 104448428 A CN104448428 A CN 104448428A CN 201310421957 A CN201310421957 A CN 201310421957A CN 104448428 A CN104448428 A CN 104448428A
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
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- 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
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Abstract
The present invention relates to a low VOC content expansion vibration-reduction rubber, and belongs to the technical field of expansion vibration-reduction. A purpose of the present invention is mainly to solve the problem of high VOC content in the existing expansion vibration-reduction rubber. The low VOC content expansion vibration-reduction rubber is mainly characterized by comprising 10-40 parts of liquid polybutadiene, 2-10 parts of a solid rubber, 5-15 parts of a plasticizer, 3-10 parts of sulfur, 2-10 parts of an accelerator, 0.1-3 parts of an antioxidant, 1-10 parts of an activator, 0.5-3 parts of a foaming agent, 0-1 part of a pigment, and 30-60 parts of a filler. According to the present invention, the VOC content of the expansion vibration-reduction rubber after curing can be significantly reduced while other performances are basically unchanged, the low VOC content expansion vibration-reduction rubber can be widely used for welding and filling between the outer plate and the strengthening beam of the welding wire vehicle body covering member so as to provide the buffer vibration-reduction effect, and volatiles and precipitates do not exist so as not to cause adverse effects on the vehicle body compartment odor.
Description
Technical field
The invention belongs to expansion shock-reducing rubber technical field.Be specifically related to a kind of expansion shock-reducing rubber of low VOC content.
Background technology
In body of a motor car manufacturing processed, combination between the outside plate of cover panel and strong beam uses welding process to assemble usually, as vehicle body lid of cab strong beam, engine bonnet strong beam and luggage-boot lid strong beam etc. and the combination of outside plate, all take welding process.Owing to there is certain gap between cover plate and strong beam, in traveling, noise may be produced because of vibration, and the solder joint on cover plate also seriously destroys the planarization of outward appearance.For overcoming above shortcoming, can before being welded, expanded polystyrene veneer shock-reducing rubber stick is coated in drawing quality steel sheet and strong beam structure, after paint drying equipment is heating and curing, glue-line has higher bonding strength, combines closely integral after expanded by heating by strong beam and cover plate, less or fully phase out in conjunction with solder joint, the aesthetic property of vehicle body appearance can be improved, weaken the vibration in driving and noise.
Along with the continuous growth of China's automobile pollution, automobile and daily life relation are more close, and meanwhile, the concern that in-car air quality is subject to human consumer gets more and more.Attractive in appearance and the comfortable single factor being no longer interior trim and selecting, human consumers more and more pay close attention to car internal medium, low smell has also become the principal concern purchasing car, so for main engine plants, low smell, the low material distributed will attract more human consumer, this is self-evident for its brand image of lifting, and for downstream supplier, low VOC represents less volatile matter and precipitate, for operating environment improvement, to reduce the cleaning frequency of mould and the stability of post-treatment be all very important.
At present, the research of all not mentioned expansion shock-reducing rubber such as domestic and international patent in low VOC content, the expansion shock-reducing rubber formula disclosing a kind of low VOC content of the present invention's innovation and preparation method.
Summary of the invention
The present invention is directed to above-mentioned and provide one obviously can reduce expansion shock-reducing rubber VOC content, meet volatile organic content TVOC(≤nC20)≤800 μ g/g, volatile organic content TVOC(≤nC16)≤500 μ g/g, benzene content≤5 μ g/g, toluene level≤5 μ g/g, butylacetate content≤5 μ g/g, ethyl-benzene level≤5 μ g/g, xylene content≤10 μ g/g, styrene content≤3 μ g/g, santochlor content≤3 μ g/g, the requirement of carbon undecane content≤3 μ g/g, the volatile organic compounds (VOC) meeting material in automobile cabin is analyzed.
Technical solution of the present invention is: a kind of expansion shock-reducing rubber of low VOC content, is characterized in that: the ratio of weight and number of described composition is as follows:
Liquid polybutadiene 10-40 part;
Solid rubber 2-10 part;
Softening agent 5-15 part;
Sulphur 3-10 part;
Promotor 2-10 part;
0.1-3 part, oxidation inhibitor;
Promoting agent 1-10 part;
Whipping agent 0.5-3 part;
Pigment 0-1 part;
Filler 30-60 part.
The preferred technical solution of the present invention is: a kind of expansion shock-reducing rubber of low VOC content, is characterized in that: the ratio of weight and number of described composition is as follows:
Liquid polybutadiene 20-30 part;
Solid rubber 3-8 part;
Softening agent 7-12 part;
Sulphur 5-10 part;
Promotor 2-8 part;
Oxidation inhibitor 0.2-2.5 part;
Promoting agent 2-8 part;
Whipping agent 1-2 part;
Pigment 0-1 part;
Filler 40-50 part.
The liquid polybutadiene described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is at least one liquid polybutadiene with the Isosorbide-5-Nitrae-cis-double bonds being less than the ethylene double bond of 5%, the Isosorbide-5-Nitrae-trans double bond of 20-25% and 75-80%.
The solid rubber described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is Isosorbide-5-Nitrae-cis-polybutadiene rubber (cis-1,4-polybutadiene rubber), styrene butadiene rubbers (styrene-butadiene rubber(SBR)) or its mixture.
The softening agent described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is benzene sulfonamide acid esters, dioctyl sebacate, triethylene glycol two 2-ethylhexoate or its mixture.
The promotor described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is thiuram-disulfide, benzothiazyl disulfide, guanidine or its mixture.
The oxidation inhibitor described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (irgasfos 168), 2,2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol) (antioxidant 2246) or its mixture.
The promoting agent described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is zinc oxide, calcium oxide, stearic acid or its mixture.
The whipping agent described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is chemical foaming agent, expended microsphere or its mixture.
The chemical foaming agent described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is azo-compound, oxynitroso salt derivative, benzol sulfohydrazide class or its mixture.
The pigment described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention is titanium dioxide, carbon black, graphite or its mixture.
The filler described in expansion shock-reducing rubber technical solution of a kind of low VOC content of the present invention be superfine calcium carbonate, mica powder, silica powder, diatomite, kaolin, silicon powder, through stearic acid or silane coupling agent surface-treated Paris white or its mixture.
The expansion shock-reducing rubber of a kind of low VOC content of the present invention, by adding appropriate solid rubber, auxiliary agent and filler in liquid polybutadiene rubber, has prepared a kind of expansion shock-reducing rubber of low VOC content.
The expansion shock-reducing rubber of a kind of low VOC content prepared by the present invention, is widely used in the outside plate of welding line cover panel with bonding between strong beam with fill, plays the effect of buffer shock-absorbing.The expansion shock-reducing rubber of a kind of low VOC content prepared by the present invention than general expansion shock-reducing rubber volatile matter and can precipitate low, guarantee the safety of vehicle to personnel by bus.
Accompanying drawing explanation
Fig. 1 is the schematic diagram (cohesive failure in the middle of glue-line fracture deflection) of shearing resistance fractured appearance interfacial failure form one, RC (0%RA).
Fig. 2 is the schematic diagram (cohesive failure of a glue-line fracture deflection bonding plane) of shearing resistance fractured appearance interfacial failure form two, RCS (0%RA).
Fig. 3 is the schematic diagram (glue-line breaks at the interfacial failure that a bonding plane comes off) of shearing resistance fractured appearance interfacial failure form three, RA (100%RA).
Embodiment
The following example introduces the present invention more in detail, but the present invention is not limited to this.
More fully description is made to the present invention now with reference to embodiment.Unless otherwise noted, " part " otherwise in embodiment all refers to weight part.
The seal gum that following evaluation obtains in an embodiment, the result of embodiment contrast is as table one, and table two, table three, shown in table four.
(1) shearing resistance:
With the clean galvanized steel sheet of washed with heptane (galvanized steel sheet size 100 × 25 × 0.8mm), dry 30 minutes, to be immersed in slushing oil (FERROCOAT 6130N machine oil and normal heptane by volume 1:9 preparation) 2 minutes, vertically hang 30 minutes after taking out, vertically stand on toilet paper upper 2 minute, for subsequent use.
The galvanized steel sheet of cleaning oiling fixes PTFE pad (shim size 30 × 25 × 2mm), applying glue between pad, and assembling steel disc makes glue uniform adhesion (glue-line is of a size of 25 × 12.5 × 2mm) between two test pieces, fixes test piece with fixture.
Answer horizontal positioned after test piece gluing, be cured by 170 DEG C × 25min.After drying or cooling, take out PTFE pad.Test plate (panel) is placed after 24 hours in thermostatic chamber environment, is known by unnecessary glue with blade, for subsequent use.
Tensile shear mensuration is carried out, record shearing resistance and fractured appearance with reference to GB/T 7174-1986 standard.
(2) hydrothermal aging test:
Test specimen absorbent cotton after solidification is wrapped in rear loading polyethylene packet, adds the deionized water being equivalent to absorbent cotton 10 times of weight, extrude the air in pouch to greatest extent, and smooth with hand, sealed polyethylene pouch.
The polyethylene packet sealed being put into 70 DEG C of baking ovens starts aging, takes out test piece and blob of viscose after 21 days from pouch and absorbent cotton, test piece and blob of viscose is put into-20 DEG C of refrigerators and continues 2h, place under room temperature until dry subsequently.
Tensile shear test is carried out, record shearing resistance and fractured appearance with reference to GB/T 7174-1986 standard.
(3) cure conditions:
170℃*25min。
(4) interfacial failure form as shown in Figure 1, Figure 2, Figure 3 shows.
(5) VOC test: volatile organic content TVOC(≤nC20)≤800 μ g/g, volatile organic content TVOC(≤nC16)≤500 μ g/g, benzene content≤5 μ g/g, toluene level≤5 μ g/g, butylacetate content≤5 μ g/g, ethyl-benzene level≤5 μ g/g, xylene content≤10 μ g/g, styrene content≤3 μ g/g, santochlor content≤3 μ g/g, carbon undecane content≤3 μ g/g.
(6) aldehyde, ketone test: formaldehyde content≤0.3 μ g/g, acetaldehyde≤0.1 μ g/g, level of acrolein≤0.1 μ g/g, acetone content≤5 μ g/g, propionic aldehyde content (μ g/g) 0, crotonaldehyde content (μ g/g) 0, methacrylic aldehyde (μ g/g) 0,2-butanone content (μ g/g) 0, butyraldehyde content (μ g/g) 0, phenyl aldehyde content (μ g/g) 0, valeral content (μ g/g) 0, p-tolyl aldehyde content (μ g/g) 0, hexanal content (μ g/g) 0.
Embodiment 1: liquid polybutadiene 10 parts, cis-1,4-polybutadiene rubber (solid) 2 parts, phenyl alkylsulf 5 parts, 3 parts, sulphur, altax 2 parts, antioxidant 2246 0.1 part, 0.5 part, calcium oxide, 0.5 part, zinc oxide, 4,4'-OBSH (OBSH) 0.5 part, carbon black 0 part, 14 parts, surface stearic acid process calcium carbonate, calcium carbonate 16.
Embodiment 2: liquid polybutadiene 20 parts, 3 parts, styrene-butadiene rubber(SBR) (solid), phenyl alkylsulf 10 parts, 5 parts, sulphur, altax 4 parts, antioxidant 2246 0.5 part, 1.5 parts, calcium oxide, 1.5 parts, zinc oxide, 4,4'-OBSH (OBSH) 1 part, carbon black 0.4 part, 22 parts, surface treatment calcium carbonate, 18 parts, calcium carbonate.
Embodiment 3: liquid polybutadiene 30 parts, cis-1,4-polybutadiene rubber (solid) 6 parts, phenyl alkylsulf 12 parts, 8 parts, sulphur, altax 6 parts, antioxidant 2246 2 parts, 3 parts, calcium oxide, 3 parts, zinc oxide, 4,4'-OBSH (OBSH) 2 parts, carbon black 0.8 part, 30 parts, surface treatment calcium carbonate, calcium carbonate 20.
Embodiment 4: liquid polybutadiene 40 parts, cis-1,4-polybutadiene rubber (solid) 10 parts, phenyl alkylsulf 15 parts, 10 parts, sulphur, altax 10 parts, antioxidant 1010 3 parts, 5 parts, calcium oxide, 5 parts, zinc oxide, 4,4'-OBSH (OBSH) 3 parts, carbon black 1 part, 40 parts, surface treatment calcium carbonate, calcium carbonate 20.
Embodiment 5: liquid polybutadiene 20 parts, cis-1,4-polybutadiene rubber (solid) 5 parts, phenyl alkylsulf 10 parts, 8 parts, sulphur, altax 2.5 parts, oxidation inhibitor LC 2 parts, 4 parts, calcium oxide, 2 parts, zinc oxide, 4,4'-OBSH (OBSH) 1 part, carbon black 1 part, 25 parts, surface treatment calcium carbonate, calcium carbonate 20.
Embodiment 6: liquid polybutadiene 30 parts, cis-1,4-polybutadiene rubber (solid) 6 parts, phenyl alkylsulf 15 parts, 10 parts, sulphur, altax 3 parts, antioxidant 2246 2 parts, 4 parts, calcium oxide, 2 parts, zinc oxide, 4,4'-OBSH (OBSH) 1.5 parts, carbon black 1 part, 30 parts, surface treatment calcium carbonate, calcium carbonate 20.
Above-described embodiment is respectively got material according to formula, material is dropped into opening rubber mixing machine and plasticates, cross three roller grindings, then return in planetary mixer and stir, after deaeration, obtain expansion shock-reducing rubber.
As can be seen from table one and table two, embodiment 1 ~ embodiment 6 traditional performance and aged properties all meet the general standard of weld car shock-reducing rubber, can use as weld car polar expansion shock-reducing rubber.
As can be seen from table three and table four, VOC tests 11, and aldehyde ketone tests 13, and embodiment 1 ~ embodiment 6 all properties all meets the demands, and especially embodiment 5 and embodiment 6 are better than embodiment 1 ~ embodiment 4.
Claims (12)
1. an expansion shock-reducing rubber for low VOC content, is characterized in that: the ratio of weight and number of described composition is as follows:
Liquid polybutadiene 10-40 part;
Solid rubber 2-10 part;
Softening agent 5-15 part;
Sulphur 3-10 part;
Promotor 2-10 part;
0.1-3 part, oxidation inhibitor;
Promoting agent 1-10 part;
Whipping agent 0.5-3 part;
Pigment 0-1 part;
Filler 30-60 part.
2. the expansion shock-reducing rubber of a kind of low VOC content according to claim 1, is characterized in that: the ratio of weight and number of described composition is as follows:
Liquid polybutadiene 20-30 part;
Solid rubber 3-8 part;
Softening agent 7-12 part;
Sulphur 5-10 part;
Promotor 2-8 part;
Oxidation inhibitor 0.2-2.5 part;
Promoting agent 2-8 part;
Whipping agent 1-2 part;
Pigment 0-1 part;
Filler 40-50 part.
3. the expansion shock-reducing rubber of a kind of low VOC content according to claim 1, it is characterized in that: described liquid polybutadiene has to be less than the ethylene double bond of 5%, 1 of 20-25%, the at least one liquid polybutadiene of the Isosorbide-5-Nitrae-cis-double bonds of 4-trans double bond and 75-80%.
4. the expansion shock-reducing rubber of a kind of low VOC content according to claim 1, is characterized in that: described solid rubber is Isosorbide-5-Nitrae-cis-polybutadiene rubber (cis-1,4-polybutadiene rubber), styrene butadiene rubbers (styrene-butadiene rubber(SBR)) or its mixture.
5. the expansion shock-reducing rubber of a kind of low VOC content according to claim 1, is characterized in that: described softening agent is benzene sulfonamide acid esters, dioctyl sebacate, triethylene glycol two 2-ethylhexoate or its mixture.
6. the expansion shock-reducing rubber of a kind of low VOC content according to claim 1, is characterized in that: described promotor is thiuram-disulfide, benzothiazyl disulfide, guanidine or its mixture.
7. the expansion shock-reducing rubber of a kind of low VOC content according to claim 1, it is characterized in that: described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 2,2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol) or its mixture.
8. the expansion shock-reducing rubber of a kind of low VOC content according to claim 1, is characterized in that: described promoting agent is zinc oxide, calcium oxide, stearic acid or its mixture.
9. the expansion shock-reducing rubber of a kind of low VOC content according to claim 1, is characterized in that: described whipping agent is chemical foaming agent, expended microsphere or its mixture.
10. the expansion shock-reducing rubber of a kind of low VOC content according to claim 7, is characterized in that: described chemical foaming agent is azo-compound, oxynitroso salt derivative, benzol sulfohydrazide class or its mixture.
The expansion shock-reducing rubber of 11. a kind of low VOC contents according to claim 1, is characterized in that: described pigment is titanium dioxide, carbon black, graphite or its mixture.
The expansion shock-reducing rubber of 12. a kind of low VOC contents according to claim 1, is characterized in that: described filler be superfine calcium carbonate, mica powder, silica powder, diatomite, kaolin, silicon powder, through stearic acid or silane coupling agent surface-treated Paris white or its mixture.
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| CN201310421957.9A CN104448428A (en) | 2013-09-13 | 2013-09-13 | Low VOC content expansion vibration-reduction rubber |
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| CN201310421957.9A CN104448428A (en) | 2013-09-13 | 2013-09-13 | Low VOC content expansion vibration-reduction rubber |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456347A (en) * | 2018-06-05 | 2018-08-28 | 广东天诚密封件股份有限公司 | A kind of automobile engine high pressure oil rail cushion blocking |
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| CN102516899A (en) * | 2011-12-02 | 2012-06-27 | 湖北回天胶业股份有限公司 | Expanding damping adhesive with good damp heat resistance ageing performance |
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- 2013-09-13 CN CN201310421957.9A patent/CN104448428A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181241A (en) * | 2011-04-19 | 2011-09-14 | 三友（天津）高分子技术有限公司 | Thermal expansion banded adhesive special for automobiles and preparation method thereof |
| CN102516899A (en) * | 2011-12-02 | 2012-06-27 | 湖北回天胶业股份有限公司 | Expanding damping adhesive with good damp heat resistance ageing performance |
| CN102516900A (en) * | 2011-12-02 | 2012-06-27 | 湖北回天胶业股份有限公司 | Expanding damping adhesive with good oil surface adhesive performance and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456347A (en) * | 2018-06-05 | 2018-08-28 | 广东天诚密封件股份有限公司 | A kind of automobile engine high pressure oil rail cushion blocking |
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Application publication date: 20150325 |