CN114195922B - Preparation method of polybutadiene-based flexible rapid photo-curing resin - Google Patents
Preparation method of polybutadiene-based flexible rapid photo-curing resin Download PDFInfo
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Abstract
A preparation method of polybutadiene-based flexible rapid photo-curing resin relates to a preparation method of rapid photo-curing resin. The invention aims to solve the problems that the existing hydroxyl-terminated polybutadiene resin cannot be subjected to photocuring and has poor performance after being mixed with other raw materials, and the problem that most of modified hydroxyl-terminated polybutadiene photocuring resins are low in curing speed. The preparation method comprises the following steps: firstly, pentaerythritol triacrylate and oxalyl chloride react to generate an intermediate product containing polyacrylate groups; secondly, reacting the intermediate product with hydroxyl-terminated liquid polybutadiene to obtain the polybutadiene-based flexible rapid photo-curing resin. The advantages are that: the triacrylate group at the end of the resin endows the resin with rapid photocuring performance, and the polybutadiene chain segment endows the resin with good flexibility, so that the resin has rapid curing characteristics, a molecular chain is flexible, and the viscosity of the resin is low. These characteristics endow the resin with good processability, so that the resin has great application potential in the field of 3D printing flexibility.
Description
Technical Field
The invention relates to a preparation method of a rapid light-cured resin.
Background
At present, liquid hydroxyl-terminated polybutadiene resin can only be thermally cured by virtue of hydroxyl at the molecular terminal, and has no group capable of undergoing photocuring, so that the liquid hydroxyl-terminated polybutadiene resin cannot be used as a flexible 3D printing photocuring resin. In order to make it photocurable, one method is to mix it with a uv-curable prepolymer, but the properties of the mixture obtained after mixing it with other raw materials are for the most part unsatisfactory; the other method is to modify the hydroxyl groups at two ends of the modified product, but most of the modified products at present are in a monoacrylate structure, such as acryloyl chloride, hydroxyethyl acrylate and the like, and the photocuring speed is slow, so that the processing period is long, the cost is high, the curing speed is slow, resin continuously flows to damage the structure, and the modified product is not suitable for processing molded parts with complicated and irregular shapes and is difficult to meet the requirements. In addition, the light-cured flexible resin has great application potential in the field of 3D printing, such as the textile field, the flexible electronic device field and the like.
Disclosure of Invention
The invention aims to solve the problems that the existing hydroxyl-terminated polybutadiene resin cannot be subjected to photocuring and has poor performance after being mixed with other raw materials, and the problem that most of modified hydroxyl-terminated polybutadiene photocuring resins are low in curing speed, and further provides a preparation method of the polybutadiene-based flexible and rapid photocuring resin.
A preparation method of polybutadiene-based flexible rapid photo-curing resin is carried out according to the following steps:
weighing 4 to 12 parts of pentaerythritol triacrylate, 1 to 5 parts of oxalyl chloride, 7 to 45 parts of toluene, 2 to 3 parts of triethylamine, 30 to 80 parts of hydroxyl-terminated liquid polybutadiene, 0.1 to 0.3 part of hydroquinone and 0 to 21 parts of methyl methacrylate in parts by weight;
secondly, dissolving 1 to 5 parts of oxalyl chloride in 5 to 10 parts of toluene to obtain an oxalyl chloride solution;
dissolving 4-12 parts of pentaerythritol triacrylate and 0.1-0.3 part of hydroquinone in 2-35 parts of toluene to obtain a mixed solution of the pentaerythritol triacrylate and the hydroquinone, dropwise adding the mixed solution of the pentaerythritol triacrylate and the hydroquinone into the oxalyl chloride solution under the conditions of nitrogen atmosphere and ice-water bath, and stirring for 1-3 hours under the conditions of nitrogen atmosphere, ice-water bath and stirring to obtain an intermediate product containing polyacrylate groups;
fourthly, adding 2 to 3 parts of triethylamine to 30 to 80 parts of hydroxyl-terminated liquid polybutadiene, and uniformly stirring to obtain a mixture of the triethylamine and the hydroxyl-terminated liquid polybutadiene;
and fifthly, under the conditions of nitrogen atmosphere and ice-water bath, adding the intermediate product containing polyacrylate groups into the mixture of triethylamine and hydroxyl-terminated liquid polybutadiene, reacting for 2-5 h under the conditions of nitrogen atmosphere, ice-water bath and stirring, then adding 0-21 parts of methyl methacrylate to obtain a crude product, and centrifugally drying the crude product to obtain the polybutadiene-based flexible rapid photocuring resin.
The beneficial effects of the invention are:
firstly, the characteristic that the hydroxyl-terminated liquid polybutadiene can only be thermally cured is changed, and a polyacrylate structure is used for modification, so that the rapid photocuring capability of the polybutadiene resin is endowed, and the application range of the polybutadiene resin is widened;
secondly, most of the existing modified polybutadiene light-cured resin is low in curing speed, and the resin flows while being cured in the curing process, so that the formed product is uneven in thickness and irregular in structure; the polybutadiene photocuring resin prepared by the invention has a multi-acrylate group structure at two ends, can be rapidly crosslinked and cured within 20s after being irradiated by ultraviolet light to form an elastomer, and meets the use requirement.
The prepared polybutadiene-based light-cured resin has the advantages of excellent flexibility, low viscosity and adjustability (compared with an isophorone diisocyanate-based isocyanate connecting agent, the resin viscosity of oxalyl chloride serving as the connecting agent is lower); the liquid hydroxyl polybutadiene has small acting force among molecular chains, more flexible molecular chains and lower viscosity, the viscosity of a polybutadiene photocuring resin product can be adjusted according to the amount of HTPB added in the synthesis process, and the method has great application potential in the 3D printing industry, such as the 3D printing textile field, the flexible electronic equipment field and the like, and the 3D printing resin has good flexibility and elongation at break while meeting certain mechanical properties. Besides, the coating has the advantages of better thermal stability, transparency and the like.
Drawings
FIG. 1 is a synthetic route of polybutadiene-based flexible fast photocurable resin of the present invention;
FIG. 2 is a UV-DSC curve with 1 being MHTPB-1, 2 being MHTPB-2, 3 being MHTPB-3, 4 being MHTPB-4, 6 being MHTPB-acryloyl chloride;
FIG. 3 is a flexible representation of MHTPB-4;
FIG. 4 is a comparative example of flexibility of MHTPB-1, MHTPB-2, MHTPB-3 and MHTPB-4 being bent by its own weight by an iron stand horizontally clamping them;
FIG. 5 is a graph comparing the transparency of MHTPB-1, MHTPB-2, MHTPB-3 and MHTPB-4;
FIG. 6 is a thermogravimetric plot with 1 being MHTPB-1, 2 being MHTPB-2, 3 being MHTPB-3, 4 being MHTPB-4;
FIG. 7 is a graph of a mesomeric quotient thermogravimetric curve, where 1 is MHTPB-1, 2 is MHTPB-2, 3 is MHTPB-3, and 4 is MHTPB-4;
FIG. 8 is an FTIR spectrum with 1 being MHTPB-1, 2 being MHTPB-2, 3 being MHTPB-3, 4 being MHTPB-4, 5 being HTPB;
FIG. 9 is CDCl 3 Of medium HTPB and four MHTPBs 1 H NMR spectrum, 1 is MHTPB-1, 2 is MHTPB-2, 3 is MHTPB-3, 4 is MHTPB-4, and 5 is HTPB;
FIG. 10 is a dynamic mechanical analysis curve, 1 being MHTPB-1, 2 being MHTPB-2, 3 being MHTPB-3, 4 being MHTPB-4;
FIG. 11 is a graph of loss factor versus temperature for MHTPB-1 at 1, MHTPB-2 at 2, MHTPB-3 at 3, and MHTPB-4 at 4.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of polybutadiene-based flexible rapid photocuring resin, which is carried out according to the following steps:
weighing 4 to 12 parts of pentaerythritol triacrylate, 1 to 5 parts of oxalyl chloride, 7 to 45 parts of toluene, 2 to 3 parts of triethylamine, 30 to 80 parts of hydroxyl-terminated liquid polybutadiene, 0.1 to 0.3 part of hydroquinone and 0 to 21 parts of methyl methacrylate in parts by weight;
secondly, dissolving 1 to 5 parts of oxalyl chloride in 5 to 10 parts of toluene to obtain an oxalyl chloride solution;
dissolving 4-12 parts of pentaerythritol triacrylate and 0.1-0.3 part of hydroquinone in 2-35 parts of toluene to obtain a mixed solution of the pentaerythritol triacrylate and the hydroquinone, dropwise adding the mixed solution of the pentaerythritol triacrylate and the hydroquinone into an oxalyl chloride solution under the conditions of nitrogen atmosphere and ice-water bath, and stirring for 1-3 hours under the conditions of nitrogen atmosphere, ice-water bath and stirring to obtain an intermediate product containing polyacrylate groups;
fourthly, adding 2 to 3 parts of triethylamine to 30 to 80 parts of hydroxyl-terminated liquid polybutadiene, and uniformly stirring to obtain a mixture of the triethylamine and the hydroxyl-terminated liquid polybutadiene;
and fifthly, under the conditions of nitrogen atmosphere and ice-water bath, adding the intermediate product containing polyacrylate groups into the mixture of triethylamine and hydroxyl-terminated liquid polybutadiene, reacting for 2-5 h under the conditions of nitrogen atmosphere, ice-water bath and stirring, then adding 0-21 parts of methyl methacrylate to obtain a crude product, and centrifugally drying the crude product to obtain the polybutadiene-based flexible rapid photocuring resin.
FIG. 1 is a synthetic route of polybutadiene-based flexible fast photocurable resin of the present invention; the resin synthesized by the invention is free radical type light-cured resin. After ultraviolet irradiation, the free radical type photoinitiator absorbs energy and is cracked into active free radicals, the acrylate structure at the end of the polybutadiene-based light-cured resin is activated by the active free radicals to polymerize, and unsaturated double bonds of the acrylate structure are opened to form crosslinking. Along with the reaction, the molecular weight in the system is rapidly increased, the crosslinking points are increased continuously, and the elastomer is formed. The elastomer contains a large amount of crosslinking points, so that the elastomer has better mechanical properties.
In the specific embodiment, hydroxyl-terminated polybutadiene is modified by oxalyl chloride and PETA, polyacrylate groups are introduced, and the polyacrylate structures at two ends endow the polybutadiene resin with the capability of rapid photocuring, so that the application range of the polybutadiene is expanded; the specific embodiment takes hydroxyl-terminated polybutadiene as a base material, retains the characteristic of flexibility of the hydroxyl-terminated polybutadiene, and has good application potential in the 3D printing industry.
The beneficial effects of the embodiment are as follows:
firstly, the characteristic that the hydroxyl-terminated liquid polybutadiene can only be thermally cured is changed, and a polyacrylate structure is used for modification, so that the rapid photocuring capability of the polybutadiene resin is endowed, and the application range of the polybutadiene resin is widened;
secondly, most of the existing modified polybutadiene light-cured resin is low in curing speed, and the resin flows while being cured in the curing process, so that the formed product is uneven in thickness and irregular in structure; the polybutadiene photocuring resin prepared by the invention has a multi-acrylate group structure at two ends, can be rapidly crosslinked and cured within 20s after being irradiated by ultraviolet light to form an elastomer, and meets the use requirement.
The prepared polybutadiene-based light-cured resin has the advantages of excellent flexibility, low viscosity and adjustability (compared with an isocyanate connecting agent of isophorone diisocyanate, the resin viscosity of oxalyl chloride as the connecting agent is lower); the liquid hydroxyl polybutadiene has small acting force among molecular chains, more flexible molecular chains and lower viscosity, the viscosity of a polybutadiene photocuring resin product can be adjusted according to the amount of HTPB added in the synthesis process, and the method has great application potential in the 3D printing industry, such as the 3D printing textile field, the flexible electronic equipment field and the like, and the 3D printing resin has good flexibility and elongation at break while meeting certain mechanical properties. Besides, the coating has the advantages of better thermal stability, transparency and the like.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the first step, 10 to 12 parts of pentaerythritol triacrylate, 4 to 5 parts of oxalyl chloride, 7 to 45 parts of toluene, 2 to 3 parts of triethylamine and 40 to 80 parts of hydroxyl-terminated liquid polybutadiene are weighed according to parts by mass. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: in the first step, 11.74 parts of pentaerythritol triacrylate, 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine and 46.15 parts of hydroxyl-terminated liquid polybutadiene are weighed according to parts by mass. The rest is the same as the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the first step, 11.74 parts of pentaerythritol triacrylate, 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine and 61.54 parts of hydroxyl-terminated liquid polybutadiene are weighed according to parts by mass. The others are the same as in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the first step, 11.74 parts of pentaerythritol triacrylate, 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine and 76.92 parts of hydroxyl-terminated liquid polybutadiene are weighed according to parts by mass. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the third step, the mixture is stirred for 1 to 3 hours in the nitrogen atmosphere, in the ice-water bath at the temperature of between 0 and 30 ℃ and at the stirring speed of between 300 and 600 r/min. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: in the fifth step, the reaction is carried out for 2 to 5 hours under the conditions of nitrogen atmosphere, ice water bath with the temperature of 0 to 30 ℃ and the stirring speed of 300 to 600 r/min. The others are the same as in the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: in the third step, under the conditions of nitrogen atmosphere and ice-water bath, the mixed solution of pentaerythritol triacrylate and hydroquinone is dripped into the oxalyl chloride solution at the dripping speed of 1-3 s/droplet. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and step five, reacting for 4 hours in a nitrogen atmosphere, at the temperature of 0 ℃ in an ice water bath and at the stirring speed of 600 r/min. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the centrifugal drying in the fifth step is specifically carried out according to the following steps: centrifuging at 5000r/min for 10min, filtering, and drying at 60 deg.C under-0.08 MPa for 12 hr. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a preparation method of polybutadiene-based flexible rapid photo-curing resin is carried out according to the following steps:
weighing 11.74 parts of pentaerythritol triacrylate (PETA), 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine, 46.15 parts of hydroxyl-terminated liquid polybutadiene and 0.3 part of hydroquinone in parts by mass;
secondly, dissolving 5 parts of oxalyl chloride in 5 parts of toluene to obtain an oxalyl chloride solution;
dissolving 11.74 parts of pentaerythritol triacrylate and 0.3 part of hydroquinone in 25 parts of toluene to obtain a mixed solution of the pentaerythritol triacrylate and the hydroquinone, dropwise adding the mixed solution of the pentaerythritol triacrylate and the hydroquinone into the oxalyl chloride solution at a dropwise adding speed of 1-3 s/drop under the conditions of a nitrogen atmosphere and an ice-water bath, and stirring for 3 hours under the conditions of a nitrogen atmosphere, an ice-water bath at a temperature of 0 ℃ and a stirring speed of 600r/min to obtain an intermediate product containing polyacrylate groups;
adding 3 parts of triethylamine into 46.15 parts of hydroxyl-terminated liquid polybutadiene, and uniformly stirring to obtain a mixture of triethylamine and the hydroxyl-terminated liquid polybutadiene;
and fifthly, under the conditions of nitrogen atmosphere and ice-water bath, adding the intermediate product containing polyacrylate groups into the mixture of triethylamine and hydroxyl-terminated liquid polybutadiene, reacting for 4 hours under the conditions of nitrogen atmosphere, ice-water bath at the temperature of 0 ℃ and stirring speed of 600r/min to obtain a crude product, and centrifugally drying the crude product to obtain the polybutadiene-based flexible rapid photocuring resin.
The centrifugal drying in the fifth step is specifically carried out according to the following steps: centrifuging at 5000r/min for 10min, filtering, and drying at 60 deg.C under-0.08 MPa for 12 hr.
Example two: the difference between the present embodiment and the first embodiment is: weighing 11.74 parts of pentaerythritol triacrylate (PETA), 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine, 61.54 parts of hydroxyl-terminated liquid polybutadiene and 0.3 part of hydroquinone in parts by mass. The rest is the same as the first embodiment.
Example three: the difference between the present embodiment and the first embodiment is: weighing 11.74 parts of pentaerythritol triacrylate (PETA), 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine, 76.92 parts of hydroxyl-terminated liquid polybutadiene and 0.3 part of hydroquinone in parts by mass. The rest is the same as in the first embodiment.
Example four: the difference between this comparative experiment and the first example is that: weighing 11.74 parts of pentaerythritol triacrylate (PETA), 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine, 30.77 parts of hydroxyl-terminated liquid polybutadiene, 0.3 part of hydroquinone and 20.36 parts of Methyl Methacrylate (MMA) in parts by mass; in the fifth step, the mixture is reacted for 4 hours in the nitrogen atmosphere, in the ice-water bath at the temperature of 0 ℃ and at the stirring speed of 600r/min, and then 20.36 parts of methyl methacrylate is added. The rest is the same as the first embodiment.
Comparison experiment one:
weighing 3.62 parts of acryloyl chloride, 30 parts of toluene, 3 parts of triethylamine, 30.77 parts of hydroxyl-terminated liquid polybutadiene and 0.3 part of hydroquinone in parts by weight;
secondly, adding 3 parts of triethylamine into 30.77 parts of hydroxyl-terminated liquid polybutadiene, and uniformly stirring to obtain a mixture of triethylamine and the hydroxyl-terminated liquid polybutadiene;
dissolving 3.62 parts of acryloyl chloride in 30 parts of toluene in a nitrogen atmosphere to obtain an acryloyl chloride solution;
and fourthly, adding the acryloyl chloride solution and 0.3 part of hydroquinone into the mixture of triethylamine and the hydroxyl-terminated liquid polybutadiene under the nitrogen atmosphere, and reacting for 5 hours under the conditions of the nitrogen atmosphere, the room temperature and the stirring speed of 600r/min to obtain the acryloyl chloride modified hydroxyl-terminated polybutadiene photocuring resin.
Comparative experiment two: the comparative experiment differs from the first example in that: 5 parts of oxalyl chloride from example one were replaced with 8.89 parts of isophorone diisocyanate. The rest is the same as the first embodiment.
Let hydroxyl-terminated liquid polybutadiene be abbreviated as HTPB; the polybutadiene-based flexible rapid photo-curing resin prepared in the fourth example is abbreviated as MHTPB-1, and the polybutadiene-based flexible rapid photo-curing resin prepared in the first example is abbreviated as MHTPB-2; the polybutadiene-based flexible rapid photocurable resin prepared in example II is abbreviated as MHTPB-3; the polybutadiene-based flexible rapid photocurable resin prepared in the third example is abbreviated as MHTPB-4; the polybutadiene-based flexible rapid photocuring resin prepared in the first comparative experiment is abbreviated as MHTPB-acryloyl chloride; the polybutadiene-based flexible fast photocurable resin prepared in comparative experiment two is abbreviated as MHTPB-diisocyanate.
TABLE 1 examples and comparative experiments content composition and physical properties of polybutadiene-based flexible fast photocurable resin
As can be seen from Table 1, when isophorone diisocyanate (IPDI) was used as a chain extender to modify hydroxyl terminated polybutadiene, it was found that the prepared photocurable resin had an extremely high viscosity, and rod climbing and gel formation occurred, resulting in experimental failure. The higher the content of the hydroxyl-terminated polybutadiene, the lower the viscosity, because the hydroxyl-terminated polybutadiene itself has a lower viscosity, and the higher the content, which corresponds to diluting the system, the lower the viscosity. The hydroxyl value of the polybutadiene also becomes larger with the increase of the content of hydroxyl-terminated polybutadiene, because the hydroxyl value is inevitably increased with the increase of the content of unreacted hydroxyl-terminated liquid polybutadiene in the system.
The UV curing speed and the reaction heat of the polybutadiene-based flexible rapid photo-curing resin are characterized by using UV-DSC. Weighing polybutadiene-based flexible rapid photo-curing resin, adding a photoinitiator 819, wherein the photoinitiator 819 accounts for 3% of the mass of the polybutadiene-based flexible rapid photo-curing resin, continuously stirring to dissolve the photoinitiator, then placing in vacuum to wait for bubbles to disappear, and then carrying out ultraviolet irradiation, wherein each time the ultraviolet irradiation is carried out, the ultraviolet irradiation is carried outThe sub-exposure time is 5s, the exposure is carried out once in 2min, the total exposure time is 23 times, the nitrogen atmosphere and the ultraviolet intensity are 500mW/cm 2 。
When the terminal hydroxyl group of the hydroxyl-terminated polybutadiene was modified with acryloyl chloride to have a monoacrylate group at the terminal, the viscosity of the modified product was reduced, and the photocuring rate was found to be far inferior to that of the modified product using oxalyl chloride or pentaerythritol triacrylate. The influence of different hydroxyl-terminated polybutadiene contents on the curing speed of the polybutadiene-based flexible rapid photocuring resin is found that the more HTPB, the lower the photocuring speed, and the details are as follows:
FIG. 2 is a UV-DSC curve with 1 being MHTPB-1, 2 being MHTPB-2, 3 being MHTPB-3, 4 being MHTPB-4, 6 being MHTPB-acryloyl chloride. As can be seen from FIG. 2, acryloyl chloride has a monoacrylate structure, and the modified hydroxyl-terminated polybutadiene has less initial heat release and total heat release, and the photocuring rate is relatively slow, while pentaerythritol triacrylate and oxalyl chloride modified hydroxyl-terminated polybutadiene have faster curing rate. The heat value of the primary photocuring reaction of the four modified HTPB photosensitive resins is reduced sequentially from 102J/g to 69.91J/g along with the increase of the content of the hydroxyl-terminated liquid polybutadiene. This is caused by the content difference of unsaturated acrylate structure in four modified HTPB photosensitive resin systems (MHTPB-1 > MHTPB-2 > MHTPB-3 > MHTPB-4), when the types and the contents of the photoinitiators PI are the same, the curing speed is faster when the unsaturated acrylate structure is more in the same time, and the heat value of the photocuring reaction is larger. After 23 exposures, the four modified photosensitive resins are completely cured, and the total photocuring reaction heat value is also reduced in sequence, which is also caused by the content difference of unsaturated acrylate in the four modified HTPB photosensitive resins (MHTPB-1 > MHTPB-2 > MHTPB-3 > MHTPB-4). In addition, the first four photocuring reactions are much exothermic and account for about 75% of the total curing reaction, with MHTPB-1 being as high as 80.43%, and these results indicate that the four photosensitive resins all possess fast photocuring speed and almost complete curing can be achieved within 20 s.
TABLE 2 heat value of photocuring reaction of five modified hydroxyl-terminated polybutadiene photocuring resins
MHTPB-1, MHTPB-2, MHTPB-3 and MHTPB-4 are poured into a dumbbell-shaped mold to prepare a dumbbell-shaped test piece (the middle part is 5cm multiplied by 0.5cm multiplied by 2mm) with the size of 11.5cm multiplied by 2.5cm multiplied by 2mm, and the transparency and the flexibility of the elastomer after the four polybutadiene-based light-cured resins are subjected to comparative study according to the dumbbell-shaped test piece. Weighing polybutadiene photocuring resin, adding a photoinitiator 819, wherein the photoinitiator 819 accounts for 3% of the mass of the polybutadiene photocuring resin, continuously stirring to dissolve the photoinitiator, then placing in vacuum for waiting for bubbles to disappear, taking a mercury lamp as an ultraviolet light source, and keeping the ultraviolet light intensity at 500mW/cm 2 Irradiating at room temperature 20cm away from the resin for 2 min.
Tests show that MHTPB-3 and MHTPB-4 can be folded in half without breaking, and MHTPB-1 and MHTPB-2 can be broken in the folding process and have relatively poor flexibility. FIG. 3 is a picture showing the flexibility of MHTPB-4, and it can be seen that the MHTPB-4 resin cured elastomer is bent and released again, and the MHTPB-4 resin is unbroken, which shows that the flexibility is good.
FIG. 4 is a comparative example of flexibility of MHTPB-1, MHTPB-2, MHTPB-3 and MHTPB-4 being bent by its own weight by an iron stand horizontally clamping them; as can be seen, MHTPB-1 has the lowest flexibility, MHTPB-4 has the best flexibility, and the flexibility of MHTPB elastomer is gradually increased along with the increase of the content of HTPB, because HTPB has no rigid group and has good flexibility, and the addition of the HTPB causes the reduction of the crosslinking density of the system to reduce the rigidity of the elastomer, so that MHTPB-4 has the best flexibility.
FIG. 5 is a graph showing the transparency of MHTPB-1, MHTPB-2, MHTPB-3 and MHTPB-4 in comparison. As can be seen, the four MHTPB elastomers all have good transparency, and the following fonts and patterns can still be clearly seen by using the dumbbell shape.
Thermal stability characterization is carried out on four photosensitive resins by adopting a thermogravimetric analysis method, wherein fig. 6 is a thermogravimetric weight loss curve, 1 is MHTPB-1, 2 is MHTPB-2, 3 is MHTPB-3, and 4 is MHTPB-4; FIG. 7 is a graph of rate of thermal weight loss, 1 being MHTPB-1, 2 being MHTPB-2, 3 being MHTPB-3, 4 being MHTPB-4; as can be seen, the Tg and DTG curves of the four photosensitive resins are substantially identical in shape and orientation. When the degradation of the four photosensitive resins reached 10%, the temperatures were almost all above 350 ℃, indicating that there were almost no unreacted small molecular substances in the resin system. The points of the four photosensitive resins with the fastest thermal degradation rate are consistent and are all at about 450 ℃, molecular bonds of an unsaturated acrylate structure and a polybutadiene main chain structure in a resin system are rapidly broken at the moment, and the mass loss is fastest at the moment.
FIG. 8 is an FTIR spectrum with 1 being MHTPB-1, 2 being MHTPB-2, 3 being MHTPB-3, 4 being MHTPB-4, 5 being HTPB. As can be seen, 3341cm -1 The broad absorption peak at (E) is due to stretching vibration of-OH, 2915cm -1 The absorption peak belongs to-CH 3 and-CH 2 Caused by stretching vibration of (2), 1720cm -1 The sharp absorption peak at (A) is due to the stretching vibration of-C ═ O, 1157cm -1 The absorption peak of (A) is formed by the stretching vibration of C-O-C, and finally 1636cm -1 And 813cm -1 The two absorption peaks are due to-C ═ CH 2 The comparison shows that the hydroxyl absorption peak of the HTPB resin modified by oxalyl chloride and PETA is obviously reduced, and absorption peaks of-C ═ O, -C ═ CH, C-O-C and the like different from HTPB appear.
FIG. 9 is CDCl 3 Of medium HTPB and four MHTPB 1 The H NMR spectrum showed MHTPB-1 at 1, MHTPB-2 at 2, MHTPB-3 at 3, MHTPB-4 at 4, and HTPB at 5. As can be seen from the figure, the absorption peak at a chemical shift of about 4.80 to 5.69ppm is a proton absorption peak in a C ═ C double bond structure, and the absorption peak at a chemical shift of 4.08ppm is a proton absorption peak of-OH in which-CH linked to a hydroxyl group is present 2 -has a proton absorption peak at 3.45ppm and a chemical shift absorption peak at 1.80-2.15 ppm of-CH associated with-C ═ C-double bond 2 -proton absorption peak of (a). Through comparison, after the hydroxyl terminated polybutadiene is modified, the absorption peaks at 4.80-5.69 ppm and 1.80-2.15 ppm are not changed, but the proton absorption peak of-OH at 4.08ppm almost completely disappears, and new proton absorption peaks appear at chemical shifts of 4.25, 4.63, 5.88, 6.11 and 6.38ppm, wherein the absorption peak at 4.25ppm is-CH associated with ester group 2 Absorption peak of (E), 4.63ppm is-CH linked to-O-bond 2 -and the other three absorption peaks are proton absorption peaks of unsaturated double bonds in the acrylate structure. The above results have fully demonstrated that pentaerythritol triacrylate has been completely grafted onto hydroxyl terminated polybutadiene.
FIG. 10 is a dynamic mechanical analysis curve, 1 being MHTPB-1, 2 being MHTPB-2, 3 being MHTPB-3, 4 being MHTPB-4. Wherein the storage modulus of MHTPB-1 is the highest and reaches 2290.05MPA, the storage modulus of MHTPB-3 is the lowest and is 1610.57MPa, and the storage modulus of MHTPB-1 is firstly reduced and then increased along with the increase of HTPB.
FIG. 11 is a graph of loss factor versus temperature for MHTPB-1 at 1, MHTPB-2 at 2, MHTPB-3 at 3, and MHTPB-4 at 4. As can be seen from the figure, the glass transition temperature of four MHTPB decreases from-56.37 ℃ to-62.02 ℃ with the increase of the HTPB content, the glass transition temperature is related to the structure of the crosslinking density compound, and under the condition that the structure of the compound is unchanged, the increase of HTPB reduces the relative content of the acrylate structure of MHTPB, thereby reducing the crosslinking density of the elastomer and slightly reducing Tg. For thermosets, the height of the Tan δ peak is related to the crosslink density, with higher Tan δ peaks having lower crosslink densities.
The crosslinking density of the elastomer is calculated according to a rubber elasticity theoretical formula:
wherein E' is the storage modulus of the rubber plateau area and the unit is MPa; tg is the glass transition temperature in units of ℃; r is a general gas constant, T is an absolute temperature and has a unit of K; the crosslink densities of the four MMHTPBs were calculated using the storage modulus at Tg + 40K. The mechanical properties of the four MHTPBs are specified in Table 3, from which it can be seen that the MHTPB-1 has the highest crosslinking density and the MHTPB-4 has the lowest crosslinking density, in line with the fact.
TABLE 3 mechanical Properties of the four MHTPBs
In the table a Temperature at which 10% by mass is degraded; b peak temperature of thermal degradation rate; c storage modulus; d glass transition temperature; e storage modulus at Tg + 40K; f the crosslink density.
The mechanical properties of the cured elastomers of the four MHTPB were compared and studied by tensile tests, and their flexibility was evaluated according to Young's modulus (E) and elongation at break (ε), and the effect of HTPB content on the flexibility of MHTPB elastomers was discussed, and the specific results are listed in Table 4. The magnitude of the Young's modulus marks the rigidity of the material, and the larger the Young's modulus, the less likely it will deform and the harder the object. The comparison shows that the Young modulus of MHTPB-1 is the largest because 30% of diluent MMA is added in the synthesis process, the density of acrylate groups is higher, a large number of cross-linking points are quickly formed after the acrylate groups are cured, so that the whole elastomer is harder, the density of the acrylate groups in the system is reduced along with the increase of the content of hydroxyl-terminated polybutadiene rubber, the cross-linking points of the real system are reduced, and the molecular chain movement is simpler, so that the Young modulus is smaller. The breaking elongation is also the same, with the increase of the content of hydroxyl-terminated polybutadiene rubber, the density of cross-linking points is reduced, and molecular chains are more flexible, so that the breaking elongation is gradually increased and reaches up to 20.54 +/-0.73%.
TABLE 4 Young's modulus and elongation at break of four MHTPBs
| Samples | Elongation at break (. epsilon.)%) | Young's modulus (E) (MPa) |
| MHTPB-1 | 10.64±3.80 | 39.35±10.80 |
| MHTPB-2 | 11.15±0.19 | 5.61±0.44 |
| MHTPB-3 | 14.1±2.69 | 1.89±0.04 |
| MHTPB-4 | 20.54±0.73 | 1.32±0.09 |
Claims (6)
1. A preparation method of polybutadiene-based flexible rapid photo-curing resin is characterized by comprising the following steps:
weighing 4 to 12 parts of pentaerythritol triacrylate, 1 to 5 parts of oxalyl chloride, 7 to 45 parts of toluene, 2 to 3 parts of triethylamine, 30 to 80 parts of hydroxyl-terminated liquid polybutadiene, 0.1 to 0.3 part of hydroquinone and 20.36 to 21 parts of methyl methacrylate in parts by weight;
secondly, dissolving 1 to 5 parts of oxalyl chloride in 5 to 10 parts of toluene to obtain an oxalyl chloride solution;
dissolving 4-12 parts of pentaerythritol triacrylate and 0.1-0.3 part of hydroquinone in 2-35 parts of toluene to obtain a mixed solution of the pentaerythritol triacrylate and the hydroquinone, dropwise adding the mixed solution of the pentaerythritol triacrylate and the hydroquinone into an oxalyl chloride solution under the conditions of a nitrogen atmosphere and an ice-water bath at a dropwise adding speed of 1-3 s/drop, and stirring for 1-3 hours under the conditions of a nitrogen atmosphere, an ice-water bath at a temperature of 0-30 ℃ and stirring to obtain an intermediate product containing polyacrylate groups;
fourthly, adding 2 to 3 parts of triethylamine into 30 to 80 parts of hydroxyl-terminated liquid polybutadiene, and uniformly stirring to obtain a mixture of triethylamine and the hydroxyl-terminated liquid polybutadiene;
fifthly, under the conditions of nitrogen atmosphere and ice-water bath, adding the intermediate product containing polyacrylate groups into the mixture of triethylamine and hydroxyl-terminated liquid polybutadiene, reacting for 2-5 h under the conditions of nitrogen atmosphere, ice-water bath at the temperature of 0-30 ℃ and stirring, then adding 20.36-21 parts of methyl methacrylate to obtain a crude product, and centrifugally drying the crude product to obtain the polybutadiene-based flexible rapid photo-curing resin.
2. The preparation method of polybutadiene-based flexible rapid photo-curing resin according to claim 1, wherein in step one, 10 to 12 parts of pentaerythritol triacrylate, 4 to 5 parts of oxalyl chloride, 7 to 45 parts of toluene, 2 to 3 parts of triethylamine and 40 to 80 parts of hydroxyl-terminated liquid polybutadiene are weighed according to parts by weight.
3. The method for preparing polybutadiene-based flexible rapid photo-curing resin according to claim 1, wherein in step one, 11.74 parts of pentaerythritol triacrylate, 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine and 46.15 parts of hydroxyl-terminated liquid polybutadiene are weighed according to parts by weight.
4. The method for preparing polybutadiene-based flexible rapid photo-curing resin according to claim 1, wherein in step one, 11.74 parts of pentaerythritol triacrylate, 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine and 61.54 parts of hydroxyl-terminated liquid polybutadiene are weighed according to parts by weight.
5. The method for preparing polybutadiene-based flexible rapid photo-curing resin according to claim 1, wherein in step one, 11.74 parts of pentaerythritol triacrylate, 5 parts of oxalyl chloride, 30 parts of toluene, 3 parts of triethylamine and 76.92 parts of hydroxyl-terminated liquid polybutadiene are weighed according to parts by weight.
6. The method for preparing polybutadiene-based flexible rapid photo-curing resin according to claim 1, wherein the centrifugal drying in the fifth step is specifically performed according to the following steps: centrifuging at 5000r/min for 10min, filtering, and drying at 60 deg.C under-0.08 MPa for 12 hr.
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