CN109879757A - A kind of hindered phenol damping modification agent and preparation method thereof - Google Patents
A kind of hindered phenol damping modification agent and preparation method thereof Download PDFInfo
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- CN109879757A CN109879757A CN201910099411.3A CN201910099411A CN109879757A CN 109879757 A CN109879757 A CN 109879757A CN 201910099411 A CN201910099411 A CN 201910099411A CN 109879757 A CN109879757 A CN 109879757A
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Abstract
A kind of preparation method of hindered phenol damping modification agent is by 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid or 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid and 1,12- dodecanediol, add catalyst, water entrainer carry out double esterification modification obtain.The present invention prepares hindered phenol damping modification agent synthesis and post-processing is simple and efficient, it is added in hindered phenol material, hindered phenol material over time may make not reunite, damping capacity greatly promotes, to enable hybrid damping material obtained to keep original damping capacity for a long time, stability is excellent, hindered phenol modifying agent of the present invention purity is high, impurity is few, storage process will not the moisture absorption it is rotten, product quality is suitable with when just producing after long-term placement, therefore shelf life is long, is 24 months, raw material of the present invention is easy to get, preparation process simple possible is worth marketing application.
Description
Technical field
The present invention relates to a kind of field of material technology, and in particular to a kind of hindered phenol damping modification agent and preparation method thereof.
Background technique
Polymer-based damping material (hereinafter referred damping material) is widely used in vibrating because damping property is the most prominent
Control.Traditional damping material is itself to stick based on bullet damping mechanism, only by Friction dissipation energy in strand, to damping
Performance boost ability is limited.In recent years, damping material is prepared using dynamic non-covalent key enhancing energy dissipation, it is outer in dynamic
Under power effect, non-covalent bond occurs reversible fracture and lives again, and absorbs a large amount of external energies, while molecular chain movement being caused to add
Play increases in-fighting, thus is widely deployed and applies.Current this material is primarily present in polymer/hindered phenol hydridization damping
In system, it is scattered in polymeric matrix when hindered phenol is more uniform and forms metastable intermolecular hydrogen with polymeric matrix
, it can be achieved that hybrid systems high damping when key interacts.However damping is added in developed hindered phenol damping modification agent at present
There is a problem of stability difference in material, increase with time, damping material is easy to reunite, and substantially reduces damping capacity；It is another
Aspect, hindered phenol modifying agent made from customary preparation methods still remain that impurity is more, and purity is low, and storage process is easy the moisture absorption and becomes
Matter, so that shelf life is short.
Summary of the invention
The first purpose of this invention is to provide a kind of unformed hindered phenol damping modification agent.
Second object of the present invention is to provide a kind of preparation side of above-mentioned hindered phenol damping modification agent being simple and efficient
Method.
The purpose of the present invention is what is realized by following technical measures:
A kind of hindered phenol damping modification agent, it is characterised in that: the general structure of the hindered phenol damping modification agent is as follows:
In formula, R1For methyl or tert-butyl；R2For tert-butyl.
Further, the infared spectrum of above-mentioned hindered phenol damping modification agent is in 3495cm-1、1717cm-1And 1223cm-1Position
With characteristic absorption peak.
We have found that the unformed hindered phenol modifying agent of the above structure is added in damping material, effectively in R&D process
Ground improves damping capacity, while it is excellent that no agglomeration, its modification enduring quality is used for a long time.
A kind of preparation method of hindered phenol damping modification agent, which is characterized in that it is by 3- (3- tertiary butyl-4-hydroxy -5-
Aminomethyl phenyl) propionic acid or 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid and 1,12- dodecanediol add catalysis
Agent, water entrainer carry out double esterification modification and obtain.
Further, above-mentioned 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid or 3- (3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid and 1, the molar ratio of 12- dodecanediol is 3~5:1.
Further, one of above-mentioned catalyst sulfuric acid, phosphoric acid, boric acid, hydrochloride, sulfate, p-methyl benzenesulfonic acid；Institute
Stating water entrainer is one of benzene, toluene, hexamethylene.
Further, above-mentioned catalyst is preferably p-methyl benzenesulfonic acid, dosage 1,1~5wt% of 12- dodecanediol；It is above-mentioned
Water entrainer is preferably hexamethylene, and the mass volume ratio of 1, the 12- dodecanediol and hexamethylene is 1:19~21.
Further, above-mentioned 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid is made by the following steps: Xiang Yidan
176.04g (0.3mol) antioxidant 245,96g (2.4mol) sodium hydroxide, 800~850ml distilled water, nitrogen is added in mouth bottle
Gas shielded, back hydrolysis 8h；Reaction terminates, and adopts and is extracted with dichloromethane reaction solution 4 times, uses 25ml methylene chloride every time, it
Afterwards using dilute hydrochloric acid drop reaction liquid to pH=3.00, a large amount of white precipitates are generated in the process, staticly settle 12h, take out
Filter, and repeatedly rinsed with distilled water and be precipitated to pH=7.00, it is drying to obtain.
Further, above-mentioned 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid is made from the following steps: to a single port bottle
Middle addition 58.8825g (0.05mol) antioxidant 1010,32g (0.8mol) sodium hydroxide, 200ml distilled water, 200ml acetone,
Nitrogen protection, back hydrolysis 8h；Reaction terminates, and revolving removes acetone, generates precipitating in the process, filters and removes precipitating, adopts
It is extracted with dichloromethane filtrate 4 times, uses 20ml methylene chloride every time, filtrate is titrated to pH=3.00 using dilute hydrochloric acid later,
White precipitate is generated in the process, staticly settles 12h, is filtered, and repeatedly rinsed with distilled water and be precipitated to pH=7.00, is done
It is dry to obtain the final product.
Specifically, a kind of preparation method of hindered phenol damping modification agent, it be it is obtained as follows, feature exists
In, by 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid or 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 1,
12- dodecanediol, catalyst, water entrainer are proportionally added into appropriate vessel, under inert gas protection, in 90~110 DEG C
Stirring, 60~100r/min of revolving speed react 8~10h, using fraction water device water-dividing and according to practical water yield and theoretical water outlet magnitude
Determine reaction end, reaction terminates, and uses saturated sodium bicarbonate aqueous solution drop reaction liquid pH for 7~8, using ethyl acetate
The extraction volume ratio of reaction solution after extractive titration, the ethyl acetate and reaction solution is 1:1, and liquid separation retains ethyl acetate layer, instead
It is washed with distilled water ethyl acetate layer and liquid separation again, until distilling water layer pH=7.00 after liquid separation, revolving removes ethyl acetate layer
Middle ethyl acetate obtains colorless and transparent oily fluid, and drying fluid can obtain colorless and transparent glutinous cementation body, as described unformed
Damping modification agent.
Further, above-mentioned inert gas is one of nitrogen or argon gas, and purity need to be higher than 99.99%.
Further, unformed damping modification agent obtained above is applied in hindered phenol material, may make hindered phenol material
Material will not reunite for a long time, and damping capacity greatly promotes, so that hybrid damping material obtained be enable to keep original damping for a long time
Performance, stability are excellent.
The present invention have it is following the utility model has the advantages that
Hindered phenol damping modification agent of the present invention is added in damping material, greatly promotes its damping capacity, while effectively keeping away
Exempt from the agglomeration of damping material long-time service, so that hybrid damping material can keep its damping capacity for a long time, observation
Persistently declined using 2 years all no discovery damping capacities, hybrid damping material obtained by the present invention resists relative to commercial common
Oxygen agent 245 or AO-70 system, optimal damping peak value promote about 21%, and stability is excellent.Hindered phenol damping modification of the present invention
It synthesizes and post-processes in agent preparation method and be simple and efficient, hindered phenol modifying agent purity is high obtained, impurity is few, effectively prevents
Amorphous material stores process and is easy the rotten phenomenon of the moisture absorption, it is long-term place after product quality and suitable, shelf when rigid produce
Phase is long, is 24 months, and raw material of the present invention is easy to get, preparation process simple possible, is worth marketing application.
Detailed description of the invention
Fig. 1: 1 damping modification agent infrared spectrogram of embodiment.
Fig. 2: 1 damping modification agent nucleus magnetic hydrogen spectrum figure of embodiment.
Fig. 3: 1 damping modification agent (a) of embodiment and application examples 1,2WXRD (b, c) figure.
Fig. 4: comparative example 1 (a) and application examples 1 (b), 2 (c) DMA figure.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, without departing substantially from spirit of that invention
In the case where essence, to modifications or substitutions made by the method for the present invention, step or condition, all belong to the scope of the present invention.
Embodiment 1
One, the preparation of 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid:
Addition 176.04g (0.3mol) antioxidant 245 into a 1L single port bottle, 96g (2.4mol) sodium hydroxide, 800~
850ml distilled water, nitrogen protection, back hydrolysis 8h.Reaction terminates, and adopts and is extracted with dichloromethane reaction solution 4 times, uses every time
25ml methylene chloride generates a large amount of white precipitates later using dilute hydrochloric acid drop reaction liquid to pH=3.00 in the process,
12h is staticly settled, is filtered, and repeatedly rinsed with distilled water and be precipitated to pH=7.00, it is drying precipitated up to 3- (3- tert-butyl -4-
Hydroxy-5-methyl base phenyl) propionic acid.
Two, the preparation of hindered phenol damping modification agent:
13.13g (0.065mol) 1,12- dodecanediol, 61.36g (0.26mol) are added into a 500ml single port bottle
3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid, 0.6565g p-methyl benzenesulfonic acid, 300ml hexamethylene, under nitrogen protection,
It is stirred to react 8h in 95 DEG C, revolving speed is set as 80r/min, using fraction water device water-dividing and determines reaction end, and reaction terminates, and adopts
With saturated sodium bicarbonate aqueous solution drop reaction liquid to PH=8, using reaction solution after ethyl acetate extractive titration, the acetic acid
The extraction volume ratio of ethyl ester and reaction solution is 1:1, and liquid separation retains ethyl acetate layer, is washed with distilled water ethyl acetate layer repeatedly
And liquid separation, until distilling water layer pH=7.00 after liquid separation, revolving removes ethyl acetate in ethyl acetate layer, obtains colorless and transparent
Oil-like fluid, drying fluid can obtain colorless and transparent glutinous cementation body, the as described hindered phenol damping modification agent.Embodiment 1 is made
Damping modification agent make infrared spectrogram, nucleus magnetic hydrogen spectrum figure respectively, experimental result is shown in Fig. 1, Fig. 2.
Three, the preparation of damping material:
Application examples 1: by 50g polyurethane elastomer be added mixer in mixing 2min, then be added 12.5g embodiment 1 by
Hinder the agent of phenol damping modification, continue mixing 10min, amount to mixing 12min, 185 DEG C of smelting temperature.It will be above-mentioned with vulcanizing press
Mixing sample is pressed into 1mm thin plate, and 185 DEG C of temperature, preheating time 8min, dwell time 4min.Patterned laminate is tailored with cut-off knife
At 10mm wide, 9mm long rectangle batten tests damping capacity using double cantilever beam mode.
Application examples 2: by 50g polyurethane elastomer be added mixer in mixing 2min, then be added 17.5g embodiment 1 by
Hinder the agent of phenol damping modification, continue mixing 10min, amount to mixing 12min, 185 DEG C of smelting temperature.It will be above-mentioned with vulcanizing press
Mixing sample is pressed into 1mm thin plate, and 185 DEG C of temperature, preheating time 8min, dwell time 4min.Patterned laminate is tailored with cut-off knife
At 10mm wide, 9mm long rectangle batten tests damping capacity using double cantilever beam mode.
Damping modification agent made from embodiment 1 and application examples 1,2 are subjected to WXRD detection, experimental result is shown in Fig. 3.It will
Damping material obtained routinely uses in embodiment 1,2 years is observed continuously in use process all without discovery damping capacity decline,
Therefore damping material of the present invention has good damping capacity, and stability is good, use process is not in agglomeration.
Meanwhile with the antioxidant 245 (AO-70) that can be bought currently on the market and the product that damping modification agent is not added
As a comparison case, corresponding preparation is as follows:
Comparative example 1: by 50g polyurethane elastomer be added mixer in mixing 12min, 185 DEG C of smelting temperature.Use plate
Above-mentioned mixing sample is pressed into 1mm thin plate by vulcanizer, and 185 DEG C of temperature, preheating time 8min, dwell time 4min.It will with cut-off knife
Patterned laminate is tailored into 10mm wide, and 9mm long rectangle batten tests damping capacity using double cantilever beam mode.By comparative example 1 with
Application examples 1,2 does DMA detection, as a result sees Fig. 4.After it can be seen that addition 1 damping modification agent of embodiment in DMA figure, poly- ammonia
Ester damping capacity is obviously improved, and the excellent properties can be stablized for a long time.
Comparative example 2: mixing 2min in mixer is added in 50g polyurethane elastomer, 12.5g antioxidant 245 is then added
(AO-70), continuation mixing 10min, total mixing 12min, 185 DEG C of smelting temperature.With vulcanizing press by above-mentioned mixing sample pressure
It is made 1mm thin plate, 185 DEG C of temperature, preheating time 8min, dwell time 4min.Patterned laminate is tailored into 10mm with cut-off knife
Width, 9mm long rectangle batten test damping capacity using double cantilever beam mode.Comparative example 2 and application 1 are subjected to DM, A inspection
It surveys, the comparative example 2 that antioxidant 245 (AO-70) is relatively added in 1 damping capacity of application examples after 1 damping modification agent of embodiment is added hinders
Damping properties promote 21%.
Embodiment 2
One, the preparation of 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid:
58.8825g (0.05mol) antioxidant 1010,32g (0.8mol) hydroxide are added into a 500ml single port bottle
Sodium, 200ml distilled water, 200ml acetone, nitrogen protection, back hydrolysis 8h.Reaction terminates, and revolving removes acetone, in this process
Middle generation precipitating, filters and removes precipitating, adopt and be extracted with dichloromethane filtrate 4 times, use 20ml methylene chloride every time, adopt later
Filtrate is titrated to pH=3.00 with dilute hydrochloric acid, white precipitate is generated in the process, staticly settles 12h, filter, and with distilling
Water repeatedly rinses and is precipitated to pH=7.00, drying precipitated up to 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid.
Two, the preparation of hindered phenol damping modification agent:
10.1g (0.05mol) 1,12- dodecanediol, 55.6g (0.2mol) 3- are added into a 500ml single port bottle
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 0.505g p-methyl benzenesulfonic acid, 200ml hexamethylene, under nitrogen protection, in 95 DEG C
It is stirred to react 8h, revolving speed is set as 100r/min, using fraction water device water-dividing and determines reaction end, reaction terminates, using saturation
Sodium bicarbonate aqueous solution drop reaction liquid is to pH=8.00, using reaction solution after ethyl acetate extractive titration, the ethyl acetate
Extraction volume ratio with reaction solution is 1:1, and liquid separation retains ethyl acetate layer, is washed with distilled water ethyl acetate layer repeatedly and divides
Liquid, until distilling water layer pH=7.00 after liquid separation, revolving removes ethyl acetate in ethyl acetate layer, obtains colorless and transparent oily
Fluid, drying fluid can obtain colorless and transparent glutinous cementation body, the as described hindered phenol damping modification agent.
3 damping modification agent stability experiment of embodiment
Hindered phenol damping modification agent made from Example 1,2, is placed in 40 DEG C of temperature, under the conditions of relative humidity 65%,
It places 24 months, takes a sample to check respectively at 12 months and 24 months, experimental result see the table below:
As seen from the above table, it under the conditions of corresponding experimental situation, places 24 months, product quality is just suitable with production, therefore,
This product stability is good, and shelf life is long.
The description of above example can be understood and applied the invention for the ease of those skilled in the art.It is ripe
Knowing those skilled in the art readily can make modification to examples detailed above, without having to go through creative labor.Therefore,
The present invention is not limited to embodiments here.
Claims (7)
1. a kind of hindered phenol damping modification agent, it is characterised in that: the general structure of the hindered phenol damping modification agent is as follows:
In formula, R1For methyl or tert-butyl；R2For tert-butyl.
2. the preparation method of hindered phenol damping modification agent as described in claim 1, which is characterized in that in 3- (3- tert-butyl -4-
Hydroxy-5-methyl base phenyl) propionic acid or 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid and 1, it is added in 12- dodecanediol
Catalyst, water entrainer carry out the modified preparation of double esterification.
3. the preparation method of hindered phenol damping modification agent as claimed in claim 2, which is characterized in that above-mentioned 3- (3- tert-butyl-
4- hydroxy-5-methyl base phenyl) propionic acid or 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid and 1,12- dodecanediol rub
You are than being 3~5:1.
4. the preparation method of hindered phenol damping modification agent as claimed in claim 3, which is characterized in that above-mentioned catalyst sulfuric acid,
One of phosphoric acid, boric acid, hydrochloride, sulfate, p-methyl benzenesulfonic acid；The water entrainer is benzene, toluene, one in hexamethylene
Kind.
5. the preparation method of hindered phenol damping modification agent as claimed in claim 4, which is characterized in that above-mentioned catalyst is preferably
P-methyl benzenesulfonic acid, dosage 1,1~5wt% of 12- dodecanediol；Above-mentioned water entrainer is preferably hexamethylene, 1, the 12- 12
The mass volume ratio of alkane glycol and hexamethylene is 1:19~21.
6. the preparation method of hindered phenol damping modification agent as claimed in claim 5, it be it is obtained as follows, feature exists
In, by 3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionic acid or 3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 1,
12- dodecanediol, catalyst, water entrainer are proportionally added into appropriate vessel, under inert gas protection, in 90~110 DEG C
Stirring, 60~100r/min of revolving speed react 8~10h, using fraction water device water-dividing and according to practical water yield and theoretical water outlet magnitude
Determine reaction end, reaction terminates, and saturated sodium bicarbonate aqueous solution drop reaction liquid pH is used to extract using ethyl acetate for 7~8
Reaction solution after titration is taken, the extraction volume ratio of the ethyl acetate and reaction solution is 1:1, and liquid separation retains ethyl acetate layer, repeatedly
It is washed with distilled water ethyl acetate layer and liquid separation, until distilling water layer pH=7.00 after liquid separation, revolving is removed in ethyl acetate layer
Ethyl acetate, obtains colorless and transparent oily fluid, and drying fluid can obtain colorless and transparent glutinous cementation body, the as described unformed damping
Modifying agent.
7. a kind of preparation method of hindered phenol damping modification agent as claimed in claim 6, which is characterized in that above-mentioned inert gas
For one of nitrogen or argon gas, purity need to be higher than 99.99%.
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| CN201910099411.3A CN109879757A (en) | 2019-01-31 | 2019-01-31 | A kind of hindered phenol damping modification agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910099411.3A CN109879757A (en) | 2019-01-31 | 2019-01-31 | A kind of hindered phenol damping modification agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285994A (en) * | 2020-03-23 | 2020-06-16 | 深圳倍达飞科技有限公司 | High-damping wide-damping temperature range shock absorption and energy absorption modifier and preparation method thereof |
-
2019
- 2019-01-31 CN CN201910099411.3A patent/CN109879757A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285994A (en) * | 2020-03-23 | 2020-06-16 | 深圳倍达飞科技有限公司 | High-damping wide-damping temperature range shock absorption and energy absorption modifier and preparation method thereof |
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