CN110437550A - The preparation method of the automobile-used wide temperature range butyl rubber damp composite material of high-damping - Google Patents
The preparation method of the automobile-used wide temperature range butyl rubber damp composite material of high-damping Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/32—Chemically modified polycondensates by organic acids or derivatives thereof, e.g. fatty oils
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/22—Oxides; Hydroxides of metals
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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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses the preparation methods of the wide temperature range butyl rubber damp composite material of automobile-used high-damping, it is plasticized butyl rubber on the double roll mill, it is sequentially added into filler, stearic acid, zinc oxide, TMTD, DM, sulphur, phenol-formaldehyde resin modified, it is blended uniformly, then beats triangle bag, turn refining 7 times, Bao Tong, bubble removing is removed in bottom sheet, placement for 24 hours, and it is spare that raw rubber is made；The raw rubber is vulcanized on compression molding instrument, phenol-formaldehyde resin modified is obtained and butyl rubber composite damping material is blended.Its raw material sources of the method for the present invention are abundant, method is simple；Product thermal stability, heat resistance and wear-resisting property are all greatly improved, it is possible to reduce the vibration and noise that the various mechanical equipments such as automobile generate during operation damage mechanical and human body health bring.
Description
Technical field
The invention belongs to polymer as damping material fields, and in particular to a kind of boron, linseed oil double-modification phenolic resin etc. with
Butyl rubber is blended to obtain the preparation method of butyl rubber based damping composite material.
Background technique
In the continuous operation of the equipment such as automobile and machine, most accidents and equipment damage are the vibrations caused by resonating
It is dynamic to not only break up material, the service life of material is influenced, and generate a large amount of noise, interferes people's lives and by bus body
It tests, the auditory system of human body is damaged.Traditional automobile-used damping material is made of pitch base damping material, but pitch
Thermal stability and loss of properties on aging, damping function can be lost by becoming fragile under low temperature, and damp film can become after long-term ageing under high temperature
Firmly, it decline damping capacity can, or even lose damping.In addition, there are serious environmental protection to ask for pitch base damping material
It inscribes, the polycyclic aromatic hydrocarbons such as anthracene, phenanthrene, pyrene in asphalitine containing volatilization in distress, these substances and human body Long Term Contact can generate human body
Very big harm, therefore external automobile-used damping material is more and more using synthesis macromolecule as damping fin basis material.And fourth
Base rubber (IIR) is the copolymer of isobutene and a small amount of isoprene, there is symmetrical methyl, and isobutene on polyisobutene segment
Structural unit proportion in macromolecular is greater than 97%, thus there are many macromolecular chain substituent group number, the relaxation resistance of segment
Increase, in-fighting is larger, and damping characteristics are preferable, and the substance being harmful to the human body, phenolic resin tool are not generated as damping material
There are good heat resistance and mechanical performance, raw material is easy to get, and cheap, technique production equipment is simple, is increased with blend rubber
Damping factor improves damping temperature domain and preferably selects.But the defects of there are brittleness for unmodified phenolic resin greatly, poor toughness, therefore have
Necessity study it is a kind of using abundance and meet the raw material of environmental requirement, come prepare wide temperature zone high damping and using effect and
The more stable composite damping material of performance, come replace it is ineffective used in orthodox car and to the health of people nocuousness
Pitch base damping material.
Summary of the invention
It is an object of the present invention to provide the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping, in solution
State problem.
The technical scheme is that
The preparation method of the automobile-used wide temperature range butyl rubber damp composite material of high-damping, comprising steps of
(1) it is plasticized butyl rubber on the double roll mill, is sequentially added into filler, stearic acid, zinc oxide, TMTD, DM, sulphur
Sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bubble removing is removed in bottom sheet, placement for 24 hours, are made
Raw rubber is spare；
(2) raw rubber is vulcanized on compression molding instrument, obtains phenol-formaldehyde resin modified and butyl rubber composite damping is blended
Material.
Further, mass parts are pressed in step (1), the butyl rubber is 100 parts, and phenol-formaldehyde resin modified is 10~50
Part, filler is 10~30 parts, and stearic acid is 2 parts, and zinc oxide is 5 parts, and TMTD is 2 parts, and DM is 1 part, and sulphur is 2 parts.
Further, phenol-formaldehyde resin modified described in step (1) is boron modified phenolic resin and modification of flax oil phenolic aldehyde tree
The mass ratio of rouge, the boron modified phenolic resin and modification of flax oil phenolic resin is 2:1.
Further, the boron modified phenolic resin the preparation method comprises the following steps:
(1.1) first phenol is added in three-necked flask, then warming while stirring is added boric acid, uses hydrogen to 90 DEG C
Sodium oxide molybdena reacts 2h under the conditions of 90-100 DEG C of temperature, obtains boric acid phenolic ester as catalyst；
(1.2) formaldehyde is added while stirring in Xiang Suoshu boric acid phenolic ester, is warming up to 100-110 DEG C, react 3h, stop heating
And vacuum dehydration is carried out, dehydration temperaturre is 120 DEG C, and dewatering time 45min, cooling discharging obtains boron modified phenolic resin.
Further, the molar ratio of phenol described in step (1.1) and the boric acid is 1:0.4.
Further, the quality of sodium hydroxide described in step (1.1) is the 3% of the phenol quality.
Further, the molar ratio of phenol described in step (1.2) and the formaldehyde is 1:1.3.
Further, the modification of flax oil phenolic resin the preparation method comprises the following steps:
(2.1) phenol, p-methyl benzenesulfonic acid are mixed evenly by the mass ratio of 1:0.0015~1:0.0020, fastly
It is slowly added to linseed oil by the 45%~55% of phenol quality under speed stirring, is warming up to 135~145 DEG C, after reacting 2~4h, is stopped
It only heats and is cooled to room temperature under stiring, obtain linseed oil-phenol reactant object；
(2.2) by the linseed oil-phenol reactant object heating stirring, according to linseed oil-phenol reactant amount of substance
84%~88% is added formaldehyde, and ammonium hydroxide is added according to linseed oil-phenol reactant amount of substance 3%~5% after mixing evenly, delays
Slowly 100~115 DEG C are warming up to, when yellow muddiness occurs in reactant, are cooled down, it is de- to start vacuum when 48~52 DEG C
Water stops dehydration when resin liquid becomes amber transparent, and absolute ethyl alcohol and stirring dissolution is added, is cooled to room temperature discharging, obtains flax
Oil modified phenolic resin.
Further, curing temperature described in step (2) is 160~180 DEG C, and sulfide stress is 10~13MPa, when vulcanization
Between be 20~21min.
The present invention provides the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping, advantages are as follows:
(1) it is widely used in the various vehicles such as automobile, train, aircraft and engineering machinery, for reducing automobile etc.
The vibration and noise that various mechanical equipments generate during operation damage mechanical and human body health bring；
(2) compared with the automobile-used pitch of tradition and damping mat, raw material sources of the present invention are abundant and meet environmental protection concept；
(3) compared with traditional asphalt base damping mat, the damping capacity for the butyl rubber composite damping material that the present invention obtains
More excellent, performance is more stable, and the variation of temperature influences less its performance, and does not generate in use process and have to human body
Evil substance and peculiar smell；
(4) compared with common phenolic resin modified butyl rubber damping, modified phenolic resin makes the heat of itself
Stability, heat resistance and wear-resisting property are all greatly improved, good with the compatibility of butyl rubber；
(5) composite damping material that DMA analysis obtains as the result is shown is more excellent than the damping capacity of original butyl rubber.
Detailed description of the invention
Fig. 1 is addition filler but damp composite material tan δ-T relationship figure without modified resin；
Fig. 2 is the damp composite material tan δ-T relationship figure for adding filler and phenol-formaldehyde resin modified；
Fig. 3 is the damp composite material tan δ-T relationship figure for being not added with filler but adding phenol-formaldehyde resin modified；
Fig. 4 is to be not added with filler and damp composite material tan δ-T relationship figure without phenol-formaldehyde resin modified；
Fig. 5 is the cross-section morphology figure for adding filler but the damp composite material without modified resin；
Fig. 6 is the cross-section morphology figure for adding the damp composite material of filler and phenol-formaldehyde resin modified；
Fig. 7 is the cross-section morphology figure for the damp composite material for being not added with filler but adding phenol-formaldehyde resin modified；
Fig. 8 is the cross-section morphology figure for being not added with filler and the damp composite material without phenol-formaldehyde resin modified；
Fig. 9 is the infrared spectrogram of the damp composite material obtained under different additive, wherein 1 is addition filler but nothing changes
The damp composite material of property resin；2 be the damp composite material for adding filler and phenol-formaldehyde resin modified；3 for be not added with filler but
Add the damp composite material of phenol-formaldehyde resin modified；4 be to be not added with filler and the damp composite material without phenol-formaldehyde resin modified.
Specific embodiment
Task to realize the present invention, the present invention use raw material sources boron abundant, linseed oil, phenolic resin and butyl
Rubber is modified the damping factor and damping temperature domain of butyl rubber.Butyl rubber is isobutene and a small amount of isoprene
Copolymer has symmetrical methyl on polyisobutene segment, and isobutene structural unit proportion in macromolecular is greater than 97%,
Thus there are many macromolecular chain substituent group number, and the relaxation resistance of segment increases, and in-fighting is larger, and damping characteristics are preferable, in
10 DEG C can be continued until from -60 DEG C by consuming peak, be a kind of damping material that effective efficiency area is comparatively wide, fissipation factor tan δ is with temperature
The variation of degree and change, tan δ has a maximum at -30 DEG C or so, nearby has an acromion at -55 DEG C.The acromion of low temperature corresponds to
The Tg of IIR, and be the characteristic peak of butyl rubber at -30 DEG C of peak, therefore, butyl rubber has special " liquid-liquid " transformation,
Internal Friction Peak was not only high but also wide, was a kind of more satisfactory rubber damping material.
Phenolic resin is the good material for improving butyl rubber damping factor and damping temperature domain, and boron, linseed oil have
The advantages that raw material is sufficient, and performance is stablized, cheap, linseed oil are octatecatrienoic acid glyceride, in molecular structure there are three
Unconjugated double bond, after introducing boron element in phenol-formaldehyde resin modified molecule, the three-dimensional of B-O key and boracic that high bond energy can be generated is handed over
It is coupled structure, is remarkably improved the heat resistance of resin；And linseed oil long flexible chain is introduced, play the role of intrinsic toughening, makes its flexibility
Improved, and modified phenolic resin compares the better performances and stabilization of phenolic resin, cooperates other additions
Agent can obtain the more excellent butyl rubber base damping material of performance.Here is to the detailed introduction of the present invention.
The composite damping material that a kind of boron, modification of flax oil phenolic resin are blended with butyl rubber, modified phenol
The compatibility of urea formaldehyde and butyl rubber is preferable, has micron-scale phase separation, and original linear phenol-aldehyde resin becomes figure, cooperates it
His additive improves the damping temperature domain and damping factor of butyl rubber.By mass parts, butyl rubber is blended in phenol-formaldehyde resin modified
In blend, butyl rubber accounts for 100 parts, and 10~50 parts of modified resin, 10~30 parts of filler, 2 parts of stearic acid, 5 parts of zinc oxide,
TMTD2 parts, DM1 parts, 2 parts of sulphur.It is plasticized butyl rubber on the double roll mill, and is sequentially added into filler, stearic acid, oxidation
Zinc, TMTD, DM, sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bottom sheet is placed for 24 hours
Bubble removing is removed, it is spare that raw rubber is made.Then vulcanize on compression molding instrument, 160~180 DEG C of curing temperature, sulfide stress 10~
13MPa, 20~21min of vulcanization time obtain phenol-formaldehyde resin modified and butyl rubber composite damping material are blended.
There are two types of above-mentioned phenol-formaldehyde resin modified is total, boron modified phenolic resin and modification of flax oil phenolic resin.Boron modification phenol
Urea formaldehyde the preparation method comprises the following steps: first phenol is added in three-necked flask, stir and is warming up to 90 DEG C, boric acid (benzene is then added
The molar ratio of phenol and boric acid is 1:0.4), catalyst sodium hydroxide the 3% of phenol (quality be), in 90-100 DEG C of reaction 2h,
Obtain boric acid phenolic ester；Formaldehyde (molar ratio of phenol and formaldehyde is 1:1.3) is added while stirring, is warming up to 100-110 DEG C, reaction
3h stops heating and carrying out vacuum dehydration, and dehydration temperaturre is 120 DEG C, and dewatering time 45min, cooling discharging obtains boron modification
Phenolic resin.
Modification of flax oil phenolic resin the preparation method comprises the following steps: by phenol, p-methyl benzenesulfonic acid press 1:0.0015~1:
The mass ratio of 0.0020 (0.0017) is mixed evenly, and quickly stirring is lower slow by 45%~55% (50%) of phenol quality
It is slow that linseed oil is added, it is warming up to 135~145 DEG C (140 DEG C), after reaction 2~4h (3h), stops heating and being cooled under stiring
Room temperature obtains linseed oil-phenol reactant object；By linseed oil-phenol reactant object heating stirring, according to linseed oil-phenol reactant object
Formaldehyde is added in 84%~88% (86%) of quality, after mixing evenly according to linseed oil-phenol reactant amount of substance 3%~5%
(4%) ammonium hydroxide is added, is slowly warming up to 100~115 DEG C, when yellow muddiness occurs in reactant, is cooled down, until 48~52
DEG C or so when start vacuum dehydration, when resin liquid becomes amber transparent, stop dehydration, be added absolute ethyl alcohol and stirring dissolution, it is cold
But it discharges to room temperature, obtains modification of flax oil phenolic resin.
By the wide temperature range butyl rubber damp composite material of automobile-used high-damping and the no modified resin of above method preparation and/or
The damp composite material of filler compares, and specific performance please refers to Fig. 1-9 and table 1
Table 1
From in figure and table in it can be seen that addition phenol-formaldehyde resin modified and/or the obtained damp composite material of filler its most
Big damping factor reduces, but its effective damping temperature range (temperature range of damping factor >=0.3) broadens, wherein adding modified phenolic resin
The damping temperature domain for this compound material of damping that rouge and filler obtain increases 16.8 DEG C；Add the obtained damping of phenol-formaldehyde resin modified
Its tensile strength of composite material and tearing strength all increased, and wherein tensile strength increases 3.9MPa, and tearing strength increases
3.3KN/m.The addition of filler is so that the damping temperature domain of damp composite material increases, but its tensile strength and tearing strength
Slightly reduce, this is because the filler being added be dis-reinforcing filler, when molecular chain movement, filler and matrix, filler with fill out
Friction between material is so that loss increase, so showing wider damping temperature domain, but will form centainly on the surface of filler
Combination glue resulted in the phenomenon that maximum damping factor reduces so that the ratio of raw rubber is declined, and dis-reinforcing filler with
Combination between matrix is not strong, and neutralizes orientation due to generating stress collection, so that the stretching of gained damp composite material is strong
Degree and tearing strength etc. slightly decline, but do not influence service performance totally.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, combined with specific embodiments below into
One step illustrates technical solution of the present invention.But the present invention is not limited to listed embodiments, should also be included in the present invention and be wanted
Other any well known changes in the interest field asked.
" one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one implementation of the invention
A particular feature, structure, or characteristic." in one embodiment " that different places occur in the present specification not refers both to same
A embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
Embodiment 1
Take 100 parts of butyl rubber, 10 parts of phenol-formaldehyde resin modified, 10 parts of filler, 2 parts of stearic acid, 5 parts of zinc oxide, TMTD 2
Part, 1 part of DM, 2 parts of sulphur, it is then plasticized butyl rubber on the double roll mill, and be sequentially added into filler, stearic acid, oxidation
Zinc, TMTD, DM, sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bottom sheet is placed for 24 hours
Bubble removing is removed, it is spare that raw rubber is made.Then vulcanize on compression molding instrument, 160 DEG C of curing temperature, sulfide stress 13MPa, vulcanize
Time 20min obtains phenol-formaldehyde resin modified and butyl rubber composite damping material is blended.
Embodiment 2
Take 100 parts of butyl rubber, 20 parts of phenol-formaldehyde resin modified, 10 parts of filler, 2 parts of stearic acid, 5 parts of zinc oxide, TMTD 2
Part, 1 part of DM, 2 parts of sulphur, it is then plasticized butyl rubber on the double roll mill, and be sequentially added into filler, stearic acid, oxidation
Zinc, TMTD, DM, sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bottom sheet is placed for 24 hours
Bubble removing is removed, it is spare that raw rubber is made.Then vulcanize on compression molding instrument, 170 DEG C of curing temperature, sulfide stress 12MPa, vulcanize
Time 20min obtains phenol-formaldehyde resin modified and butyl rubber composite damping material is blended.
Embodiment 3
Take 100 parts of butyl rubber, 30 parts of phenol-formaldehyde resin modified, 10 parts of filler, 2 parts of stearic acid, 5 parts of zinc oxide, TMTD 2
Part, 1 part of DM, 2 parts of sulphur, it is then plasticized butyl rubber on the double roll mill, and be sequentially added into filler, stearic acid, oxidation
Zinc, TMTD, DM, sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bottom sheet is placed for 24 hours
Bubble removing is removed, it is spare that raw rubber is made.Then vulcanize on compression molding instrument, 180 DEG C of curing temperature, sulfide stress 12MPa, vulcanize
Time 20min obtains phenol-formaldehyde resin modified and butyl rubber composite damping material is blended.
Embodiment 4
Take 100 parts of butyl rubber, 40 parts of phenol-formaldehyde resin modified, 10 parts of filler, 2 parts of stearic acid, 5 parts of zinc oxide, TMTD 2
Part, 1 part of DM, 2 parts of sulphur, it is then plasticized butyl rubber on the double roll mill, and be sequentially added into filler, stearic acid, oxidation
Zinc, TMTD, DM, sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bottom sheet is placed for 24 hours
Bubble removing is removed, it is spare that raw rubber is made.Then vulcanize on compression molding instrument, 170 DEG C of curing temperature, sulfide stress 10MPa, vulcanize
Time 20min obtains phenol-formaldehyde resin modified and butyl rubber composite damping material is blended.
Embodiment 5
Take 100 parts of butyl rubber, 50 parts of phenol-formaldehyde resin modified, 10 parts of filler, 2 parts of stearic acid, 5 parts of zinc oxide, TMTD 2
Part, 1 part of DM, 2 parts of sulphur, it is then plasticized butyl rubber on the double roll mill, and be sequentially added into filler, stearic acid, oxidation
Zinc, TMTD, DM, sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bottom sheet is placed for 24 hours
Bubble removing is removed, it is spare that raw rubber is made.Then vulcanize on compression molding instrument, 180 DEG C of curing temperature, sulfide stress 10MPa, vulcanize
Time 20min obtains phenol-formaldehyde resin modified and butyl rubber composite damping material is blended.
Embodiment 6
Take 100 parts of butyl rubber, 40 parts of phenol-formaldehyde resin modified, 20 parts of filler, 2 parts of stearic acid, 5 parts of zinc oxide, TMTD 2
Part, 1 part of DM, 2 parts of sulphur, it is then plasticized butyl rubber on the double roll mill, and be sequentially added into filler, stearic acid, oxidation
Zinc, TMTD, DM, sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bottom sheet is placed for 24 hours
Bubble removing is removed, it is spare that raw rubber is made.Then vulcanize on compression molding instrument, 170 DEG C of curing temperature, sulfide stress 12MPa, vulcanize
Time 21min obtains phenol-formaldehyde resin modified and butyl rubber composite damping material is blended.
Embodiment 7
Take 100 parts of butyl rubber, 40 parts of phenol-formaldehyde resin modified, 30 parts of filler, 2 parts of stearic acid, 5 parts of zinc oxide, TMTD 2
Part, 1 part of DM, 2 parts of sulphur, it is then plasticized butyl rubber on the double roll mill, and be sequentially added into filler, stearic acid, oxidation
Zinc, TMTD, DM, sulphur, phenol-formaldehyde resin modified are blended uniformly, then beat triangle bag, turn refining 7 times, Bao Tong, and bottom sheet is placed for 24 hours
Bubble removing is removed, it is spare that raw rubber is made.Then vulcanize on compression molding instrument, 180 DEG C of curing temperature, sulfide stress 10MPa, vulcanize
Time 20min obtains phenol-formaldehyde resin modified and butyl rubber composite damping material is blended.
Boron modified phenolic resin, the preparation method difference of modification of flax oil phenolic resin are as follows in above-mentioned 7 embodiments:
1, boron modified phenolic resin the preparation method comprises the following steps:
(1.1) first phenol is added in three-necked flask, then boric acid, the benzene is added to 90 DEG C in warming while stirring
The molar ratio of phenol and the boric acid is 1:0.4, uses sodium hydroxide as catalyst, and the quality of the sodium hydroxide is the benzene
The 3% of phenol quality reacts 2h under the conditions of 90-100 DEG C of temperature, obtains boric acid phenolic ester；
(1.2) formaldehyde is added in Xiang Suoshu boric acid phenolic ester while stirring, the molar ratio of the phenol and the formaldehyde is 1:
1.3, it is warming up to 100-110 DEG C, reacts 3h, stops heating and carrying out vacuum dehydration, dehydration temperaturre is 120 DEG C, and dewatering time is
45min, cooling discharging obtain boron modified phenolic resin.
2, modification of flax oil phenolic resin the preparation method comprises the following steps:
(2.1) phenol, p-methyl benzenesulfonic acid are mixed evenly by the mass ratio of 1:0.0015~1:0.0020, fastly
It is slowly added to linseed oil by the 45%~55% of phenol quality under speed stirring, is warming up to 135~145 DEG C, after reacting 2~4h, is stopped
It only heats and is cooled to room temperature under stiring, obtain linseed oil-phenol reactant object；
(2.2) by the linseed oil-phenol reactant object heating stirring, according to linseed oil-phenol reactant amount of substance
84%~88% is added formaldehyde, and ammonium hydroxide is added according to linseed oil-phenol reactant amount of substance 3%~5% after mixing evenly, delays
Slowly 100~115 DEG C are warming up to, when yellow muddiness occurs in reactant, are cooled down, it is de- to start vacuum when 48~52 DEG C
Water stops dehydration when resin liquid becomes amber transparent, and absolute ethyl alcohol and stirring dissolution is added, is cooled to room temperature discharging, obtains flax
Oil modified phenolic resin.
3, the mass ratio of boron modified phenolic resin and modification of flax oil phenolic resin is 2:1.
In conclusion the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping of the present invention,
Its raw material sources is abundant, method is simple；Product thermal stability, heat resistance and wear-resisting property are all greatly improved, and can subtract
The vibration and noise that the various mechanical equipments such as few automobile generate during operation damage mechanical and human body health bring.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (9)
1. the preparation method of the automobile-used wide temperature range butyl rubber damp composite material of high-damping, which is characterized in that comprising steps of
(1) be plasticized butyl rubber on the double roll mill, be sequentially added into filler, stearic acid, zinc oxide, TMTD, DM, sulphur,
Phenol-formaldehyde resin modified is blended uniformly, then beats triangle bag, turn refining 7 times, Bao Tong, and bubble removing is removed in bottom sheet, placement for 24 hours, and raw rubber is made
It is spare；
(2) raw rubber is vulcanized on compression molding instrument, obtains phenol-formaldehyde resin modified and butyl rubber composite damping material is blended.
2. the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping according to claim 1, special
Sign is: by mass parts in step (1), the butyl rubber is 100 parts, and phenol-formaldehyde resin modified is 10~50 parts, filler 10
~30 parts, stearic acid is 2 parts, and zinc oxide is 5 parts, and TMTD is 2 parts, and DM is 1 part, and sulphur is 2 parts.
3. the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping according to claim 1, special
Sign is: phenol-formaldehyde resin modified described in step (1) is boron modified phenolic resin and modification of flax oil phenolic resin, and the boron changes
Property phenolic resin and modification of flax oil phenolic resin mass ratio be 2:1.
4. the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping according to claim 3, special
Sign is, the boron modified phenolic resin the preparation method comprises the following steps:
(1.1) first phenol is added in three-necked flask, then warming while stirring is added boric acid, uses hydroxide to 90 DEG C
Sodium reacts 2h under the conditions of 90-100 DEG C of temperature, obtains boric acid phenolic ester as catalyst；
(1.2) formaldehyde is added while stirring in Xiang Suoshu boric acid phenolic ester, is warming up to 100-110 DEG C, react 3h, stop heating and go forward side by side
Row vacuum dehydration, dehydration temperaturre are 120 DEG C, and dewatering time 45min, cooling discharging obtains boron modified phenolic resin.
5. the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping according to claim 4, special
Sign is: the molar ratio of phenol described in step (1.1) and the boric acid is 1:0.4.
6. the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping according to claim 4, special
Sign is: the quality of sodium hydroxide described in step (1.1) is the 3% of the phenol quality.
7. the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping according to claim 4, special
Sign is: the molar ratio of phenol described in step (1.2) and the formaldehyde is 1:1.3.
8. the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping according to claim 3, special
Sign is, the modification of flax oil phenolic resin the preparation method comprises the following steps:
(2.1) phenol, p-methyl benzenesulfonic acid are mixed evenly by the mass ratio of 1:0.0015 ~ 1:0.0020, are quickly stirred
Mix down and be slowly added to linseed oil by the 45% ~ 55% of phenol quality, be warming up to 135 ~ 145 DEG C, after reacting 2 ~ 4h, stop heating and
It is cooled to room temperature under stirring, obtains linseed oil-phenol reactant object；
(2.2) by the linseed oil-phenol reactant object heating stirring, according to linseed oil-phenol reactant amount of substance 84% ~ 88%
Formaldehyde is added, ammonium hydroxide is added according to linseed oil-phenol reactant amount of substance 3% ~ 5% after mixing evenly, it is to slowly warm up to 100 ~
It 115 DEG C, when yellow muddiness occurs in reactant, is cooled down, starts vacuum dehydration when 48 ~ 52 DEG C, when resin liquid becomes
When amber transparent, stop dehydration, absolute ethyl alcohol and stirring dissolution is added, is cooled to room temperature discharging, obtains modification of flax oil phenolic resin.
9. the preparation method of the wide temperature range butyl rubber damp composite material of automobile-used high-damping according to claim 1, special
Sign is: curing temperature described in step (2) be 160~180 DEG C, sulfide stress be 10 ~ 13MPa, vulcanization time be 20 ~
21min。
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