Modified allyl diethylene glycol carbonate sheet for track detection and preparation method thereof

Abstract

The invention provides a modified allyldiglycol carbonate sheet for track detection and a preparation method thereof, and the modified allyldiglycol carbonate sheet is prepared by curing allyldiglycol carbonate and a comonomer as main raw materials under ultraviolet irradiation. By adding the comonomer, a radiation sensitive group can be introduced into the polymer, the crosslinking density is effectively improved, the track detection efficiency is improved, and meanwhile, the curing speed is not influenced. The ultraviolet light initiator is added for light curing, the curing speed can be effectively increased, the curing time can be effectively shortened, compared with a peroxide initiator, the method can achieve curing at the normal temperature, the reaction controllability is higher, and the prepared modified allyl diethylene glycol carbonate material is high in transmittance, excellent in mechanical property and suitable for large-scale production. The method can be used for a solid nuclear track detector, and is high in track detection efficiency and good in application prospect.

Description

Technical Field

[0001] The invention relates to the field of carbonate resins, and in particular to a modified allyl diglycol carbonate sheet for track detection and a preparation method thereof. Background Art

[0002] In the 1940s, allyl diglycol carbonate CR-39 was discovered by chemists at Columbia Chemical Laboratories in the United States. It was the 39th material in a series of polymers developed by the United States Air Force, hence the name Columbia Resin 39 (CR-39, Columbia Resin No. 39, also known as PADC).

[0003] The chemical formula of CR-39 monomer is (CH2=CHCH2OCOOCH2CH2)2O, and its chemical composition is allyl diglycol carbonate (ADC). It is a colorless, transparent liquid (similar to glycerin) and is irritating to the skin and eyes. Under the influence of heat and a catalyst, or heat and pressure, the 39 monomer undergoes polymerization, transforming into a transparent, hard substance. It is a thermosetting resin (insoluble and non-meltable).

[0004] CR-39 lenses are chemically formulated and cast from the above monomers. They are lightweight (about half the weight of glass), resistant to breakage, easily formed, and tintable. They have a reticular structure that resists softening under heat but decomposes and breaks down under intense heat. They are resistant to attack by acids, bases, and organic solvents. However, certain alkaline solvents can etch or chemically degrade the resin.

[0005] The allylic polymerization mechanism applies to CR-39. The polymerization reaction consists of three steps: initiation, propagation, and termination. In the initiation step, a free radical is first generated by the decomposition of a peroxide. It then combines with the allyl group of the CR-39 monomer, transferring its unpaired electron to the tertiary carbon atom of the group. The propagation step involves the continuous addition of allyl groups to the growing macroradical, resulting in the formation of polyallylic chains. These chains are linked together by diethylene glycol dicarbonate chains, forming a densely crosslinked three-dimensional polymer network. The growth of the polyallylic chains is halted by the termination step. The general mechanism leading to the termination of free radical polymerization is the elimination of two radicals by recombination or disproportionation, which also occurs in this system. However, the most important termination mechanism unique to the polymerization of allyl monomers is degradative chain transfer, in which the growing alkyl radical annihilates by abstracting a hydrogen atom from the monomer, ultimately producing the polymer.

[0006] The peroxide initiators used in the industrial preparation of CR39 primarily include dibenzoyl peroxide (BPO), diisopropyl peroxydicarbonate (IPP), or dicyclohexyl peroxydicarbonate (CHPC). BPO was the earliest initiator used. The polymerization temperature is controlled at around 70°C, and the production of 0.125- to 0.25-inch lenses requires approximately 70 hours. This results in a high reaction temperature and a long reaction time. The advantage of using IPP and CHPC is that the polymerization temperature does not need to be too high, being lower than that required for BPO polymerization. However, IPP and CHPC have low storage temperatures, making them dangerous to transport and therefore unavailable for laboratory purchase.

[0007] For the preparation of CR39 lenses or sheets, the industry often uses a casting polymerization method. In essence, the polymerization method used in most casting polymerizations is a bulk polymerization.

[0008] In the prior art, the conversion rate is often increased by raising the polymerization temperature, but it is difficult to cure CR-39 at a constant elevated temperature using thermal initiators (such as peroxides), which decompose into free radicals when heated. If CR-39 and IPP initiators begin to cure at too high a temperature, the rapid decomposition of the initiator, which is present at the highest concentration at the beginning of curing, can produce too many free radicals. Therefore, in a high-flow system containing a high concentration of reactive allyl groups, a large number of polymer chains will grow rapidly, generating a large amount of polymerization heat, and this heat may not be dissipated in time. The system may overheat, and temperature gradients in the polymeric material may lead to structural inhomogeneities and ultimately defects in the polymer.

[0009] Allyl polymerization is inherently highly exothermic, requiring careful, slow, and prolonged polymerization. This results in a lengthy preparation time for CR-39. During most curing processes, the overall polymerization rate of CR-39 is controlled by the initiation step, particularly by the free radicals generated during the thermal decomposition of the peroxide. However, in the later stages of curing, the fluidity of the reactants decreases dramatically due to the increase in crosslink density, slowing the polymerization rate. When the glass transition temperature of the polymerization system rises to the curing temperature, the polymerization rate effectively ceases. Consequently, further increases in temperature are required to complete the curing of CR-39, impacting the polymer's performance.

[0010] Furthermore, allyl and ADC monomers typically shrink by about 14% of their volume during solid polymer formation, and if appropriate measures are not taken, the combined effects of exotherm and shrinkage can lead to cracking of the polymer film.

[0011] CR-39 resin can usually be used as a solid nuclear track detector to detect alpha rays, but its sensitivity needs to be further improved to expand its scope of application. Summary of the Invention

[0012] Based on the above technical background, the inventors conducted intensive research and prepared a modified allyl diglycol carbonate sheet by photocuring under ultraviolet light using allyl diglycol carbonate, a modified monomer, and an ultraviolet light initiator as raw materials. This preparation method can effectively increase the curing rate, shorten the curing time, and achieve curing at room temperature. At the same time, the addition of the modified monomer can effectively increase the crosslinking density and introduce radiation-sensitive groups, which is beneficial to improving the uniformity, mechanical properties, and track detection effect of the sheet. In addition, the preparation method has a simple process, high controllability, and the resulting sheet has excellent performance and good application prospects, thus completing the present invention.

[0013] The first aspect of the present invention is to provide a modified allyl diglycol carbonate sheet for track detection. The modified allyl diglycol carbonate sheet is prepared by curing allyl diglycol carbonate, a modified monomer and a photoinitiator as main raw materials under ultraviolet light.

[0014] The second aspect of the present invention is to provide a method for preparing the modified allyl diglycol carbonate sheet for track detection according to the first aspect of the present invention, the method comprising the following steps:

[0015] Step 1: mixing raw materials including allyl diglycol carbonate, a modified monomer and a photoinitiator, and placing the mixture in a mold;

[0016] Step 2: Place the mold under an ultraviolet light source for curing to obtain a modified allyl diglycol carbonate sheet. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Shown are conversion rate test graphs for Examples 1-6;

[0018] Figure 2 The conversion rate test diagrams of Examples 7-13, Comparative Examples 1 and 2 are shown.

[0019] Figure 3 Showing the transmittance curves of the products obtained in Examples 1-6;

[0020] Figure 4 Showing the transmittance curves of the products obtained in Examples 7-13 and Comparative Examples 1 and 2;

[0021] Figure 5 Shown is a yellow index graph of the products obtained in Examples 1-6;

[0022] Figure 6 A histogram showing the yellowness index of the products obtained in Examples 7-13 and Comparative Examples 1 and 2;

[0023] Figure 7 A comparison of the bulk etch rates of the products obtained in Examples 1-6 is shown;

[0024] Figure 8 A comparison of the bulk etch rates of the products obtained in Examples 7-13 is shown;

[0025] Figure 9 Shown are the track detection efficiency diagrams of the products obtained in Examples 1-6;

[0026] Figure 10 Shown are track detection efficiency graphs for the products obtained in Examples 7-13 and Comparative Examples 1 and 2;

[0027] Figure 11 The images of the sheets obtained in Examples 1-6 after irradiation etching in the etching track test are shown;

[0028] Figure 12 The images of the sheets obtained in Examples 7 to 13 and Comparative Examples 1 and 2 after irradiation etching in the etching track test are shown. DETAILED DESCRIPTION

[0029] The present invention will be described in detail below, and the characteristics and advantages of the present invention will become clearer and more distinct with the following description.

[0030] The first aspect of the present invention is to provide a modified allyl diglycol carbonate sheet for track detection, which is prepared by curing allyl diglycol carbonate, a modified monomer and a photoinitiator as main raw materials under ultraviolet light.

[0031] In the present invention, the modified monomer is selected from (meth) acrylate monomers, such as one or more of the following: triethylene glycol dimethacrylate (TEDMA), diethylene glycol dimethacrylate (DEGMA), diallyl phthalate (DAP), diallyl terephthalate (DATP), neopentyl glycol diacrylate (NPGDA), ethylene glycol dimethacrylate (EGDMA), tripropylene glycol diacrylate (BPA-DA), ethoxylated trimethylolpropane triacrylate (ETPTA), tripropylene trimellitate (TMPTA), tripropylene glycol diacrylate (BPA-DA), ethylene glycol dimethacrylate (EGDMA), tripropylene glycol diacrylate (BPA-DA ... Ester (TRAIM-705), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), trimethylolpropane trimethacrylate (TMPTMA), glyceryl trihydroxypropyl ether triacrylate (GPTA), ditrimethylolpropane tetraacrylate (DI-TMPAT), pentaerythritol tetraacrylate (PET4A), polydipentaerythritol pentaacrylate (PTMPT), polydipentaerythritol hexaacrylate (DPHA) and 2,4,6-triallyloxy-1,3,5-triazine (TAC).

[0032] In the present invention, the cross-linking degree and radiation sensitivity of the polymer can be effectively improved by selecting the modified monomer used.

[0033] The inventors discovered that existing photocuring methods for preparing allyl diglycol carbonate sheets, due to the rapid free radical polymerization reaction, tend to result in rapid product chain growth, but the polymer's radiation sensitivity needs to be improved. Experiments have shown that adding an appropriate amount of the aforementioned modifying monomer can effectively enhance the polymer sheet's radiation sensitivity and mechanical properties, thereby improving track detection efficiency.

[0034] In a preferred embodiment, the molar ratio of the modified monomer to allyl diglycol carbonate is (0.001-0.2):1, preferably (0.001-0.15):1, and more preferably (0.002-0.1):1.

[0035] In the present invention, the photoinitiator used is an ultraviolet photoinitiator, which is selected from one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone (i.e., 1173), benzoin dimethyl ether, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone and 2,4,6-trimethylbenzoyldiphenoxide, preferably one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexyl phenyl ketone.

[0036] Compared with the polymerization reaction using peroxide initiators, experiments have found that the use of the above-mentioned ultraviolet light initiator for ultraviolet polymerization can achieve room temperature polymerization, prevent thermal runaway, avoid initiator deactivation caused by heating, effectively improve the conversion rate and curing rate, and shorten the curing time.

[0037] In a preferred embodiment, the mass ratio of the ultraviolet light initiator to allyl diglycol carbonate is (0.01-0.2):1, preferably (0.02-0.15):1, and more preferably (0.04-0.1):1.

[0038] In a preferred embodiment of the present invention, the allyl diglycol carbonate sheet is prepared by the following steps:

[0039] Step 1: mixing raw materials including allyl diglycol carbonate, a modified monomer, and a photoinitiator, and placing the mixture in a mold;

[0040] Step 2: placing the mold under an ultraviolet light source for curing to obtain an allyl diglycol carbonate sheet.

[0041] Typically, the curing temperature is 20 to 30°C, preferably 20 to 25°C.

[0042] In particular, the curing reaction can be carried out at room temperature.

[0043] Preferably, the curing reaction time is 10 to 60 minutes, preferably 15 to 50 minutes, and more preferably 20 to 45 minutes.

[0044] The modified allyl diglycol carbonate sheet obtained by the invention has a high transmittance of more than 85% and a low yellow index of less than 5.

[0045] A second aspect of the present invention is to provide a method for modifying an allyl diglycol carbonate sheet for track detection, the method comprising the following steps:

[0046] Step 1: mixing raw materials including allyl diglycol carbonate, a modified monomer, and an ultraviolet light initiator, and placing the mixture in a mold;

[0047] Step 2: Place the mold under an ultraviolet light source for curing to obtain a modified allyl diglycol carbonate sheet.

[0048] This step is described and explained in detail below.

[0049] Step 1: Mix raw materials including allyl diglycol carbonate, a modified monomer and a photoinitiator, and place them in a mold.

[0050] Wherein, the modified monomer is selected from triethylene glycol dimethacrylate (TEDMA), diethylene glycol dimethacrylate (DEGMA), diallyl phthalate (DAP), diallyl terephthalate (DATP), neopentyl glycol diacrylate (NPGDA), ethylene glycol dimethacrylate (EGDMA), tripropylene glycol diacrylate (BPA-DA), ethoxylated trimethylolpropane triacrylate (ETPTA), trimellitic acid tripropylene ester (TRAIM-705), trimethylolpropane triacrylate (ETPTA), tripropylene glycol triacrylate (TRAIM-705), trimethylolpropane triacrylate (ETPTA), tripropylene glycol triacrylate (TEDMA ... One or more of propane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), trimethylolpropane trimethacrylate (TMPTMA), glycerol trihydroxypropyl ether triacrylate (GPTA), ditrimethylolpropane tetraacrylate (DI-TMPAT), pentaerythritol tetraacrylate (PET4A), polydipentaerythritol pentaacrylate (PTMPT), polydipentaerythritol hexaacrylate (DPHA) and 2,4,6-triallyloxy-1,3,5-triazine (TAC).

[0051] The molar ratio of the modified monomer to allyl diglycol carbonate is (0.001-0.2):1, preferably (0.001-0.15):1, and more preferably (0.002-0.1):1.

[0052] The ultraviolet light initiator is selected from one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone (i.e., 1173), benzoin dimethyl ether, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone and 2,4,6-trimethylbenzoyldiphenoxide, preferably one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxycyclohexyl phenyl ketone.

[0053] The mass ratio of the ultraviolet light initiator to allyl diglycol carbonate is (0.01-0.2):1, preferably (0.02-0.15):1, and more preferably (0.04-0.1):1.

[0054] The present inventors have found that when the amount of ultraviolet initiator added is within the above range, a higher monomer conversion rate can be achieved in a shorter time without affecting the transmittance, yellowness index and other properties of the prepared sheet.

[0055] Step 2: Place the mold under an ultraviolet light source for curing to obtain a modified allyl diglycol carbonate sheet.

[0056] Typically, the curing temperature is 20 to 30°C, preferably 20 to 25°C, and the polymerization reaction can be carried out at room temperature.

[0057] Preferably, the curing time is 10 to 60 minutes, preferably 15 to 50 minutes, and more preferably 20 to 45 minutes.

[0058] Preferably, the power of the ultraviolet light source is 20 to 100W, preferably 30 to 60W.

[0059] Preferably, the distance between the mold and the ultraviolet light source is 5 to 30 cm, preferably 8 to 20 cm.

[0060] The experiment found that when the power of the ultraviolet light source and the distance from the mold are adjusted to the above range, it is beneficial to improve the curing rate and further shorten the curing time.

[0061] By adding the above-mentioned ultraviolet light initiator and curing under ultraviolet light, the curing rate can be effectively increased, the curing time can be shortened, and the preparation efficiency of the allyl diglycol carbonate sheet can be improved.

[0062] The third aspect of the present invention is to provide an application of the modified allyl diglycol carbonate sheet according to the first aspect of the present invention or the modified allyl diglycol carbonate sheet prepared by the method according to the second aspect of the present invention, which can be used as a solid nuclear track detector material.

[0063] The present invention has the following beneficial effects:

[0064] (1) The preparation method of the modified allyl diglycol carbonate sheet of the present invention is simple. The reaction can be carried out at room temperature under ultraviolet light irradiation without heating, and the reaction is highly controllable.

[0065] (2) The preparation method of the present invention has a fast reaction speed and can achieve a high conversion rate in a short reaction time. The reaction time is short and the reaction can be completed in only tens of minutes, which greatly improves the preparation efficiency;

[0066] (3) The modified allyl diglycol carbonate sheet of the present invention has high transmittance, low yellow index, high mechanical properties, low preparation cost, is suitable for solid nuclear track detectors, has high track detection efficiency, and has good application prospects.

[0067] Example

[0068] The present invention is further described below through specific examples. These examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention.

[0069] Example 1

[0070] At room temperature and pressure, 25 g of allyl diglycol carbonate, 0.274 g of tripropylene glycol diacrylate (BPA-DA) (the molar ratio of allyl diglycol carbonate added is 1:100) and 1.25 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) were mixed evenly and placed in a glass mold.

[0071] The mold was then placed under a UV lamp with a power of 50 W and a wavelength of 365 nm for reaction for 25 minutes at room temperature, with the distance between the mold and the UV lamp being 10 cm.

[0072] Example 2

[0073] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the amount of tripropylene glycol diacrylate added was 0.548 g (the molar ratio to the amount of allyl diglycol carbonate added was 2:100).

[0074] Example 3

[0075] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the amount of tripropylene glycol diacrylate added was 0.821 g (the molar ratio to the allyl diglycol carbonate added was 100:3).

[0076] Example 4

[0077] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the amount of tripropylene glycol diacrylate added was 1.095 g (the molar ratio to the amount of allyl diglycol carbonate added was 4:100).

[0078] Example 5

[0079] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the amount of tripropylene glycol diacrylate added was 1.369 g (the molar ratio to the amount of allyl diglycol carbonate added was 5:100).

[0080] Example 6

[0081] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the amount of tripropylene glycol diacrylate added was 1.643 g (the molar ratio to the amount of allyl diglycol carbonate added was 6:100).

[0082] Example 7

[0083] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the modifying monomer was replaced with ethoxylated trimethylolpropane triacrylate (ETPTA) in an amount of 1.562 g (the molar ratio to the added amount of allyl diglycol carbonate was 4:100).

[0084] Example 8

[0085] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the modifying monomer was replaced with trimethylolpropane triacrylate (TMPTA) in an amount of 1.080 g (the molar ratio to the added amount of allyl diglycol carbonate was 4:100).

[0086] Example 9

[0087] A modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the modifying monomer was replaced with pentaerythritol triacrylate (PETA) in an amount of 0.816 g (the molar ratio to the added allyl diglycol carbonate was 3:100).

[0088] Example 10

[0089] A modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the modifying monomer was replaced with pentaerythritol tetraacrylate (PET4A) in an amount of 0.963 g (the molar ratio to the added allyl diglycol carbonate was 3:100).

[0090] Example 11

[0091] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the modified monomer was replaced with polydipentaerythritol pentaacrylate (PTMPT) in an amount of 0.956 g (the molar ratio to the added amount of allyl diglycol carbonate was 2:100).

[0092] Example 12

[0093] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the modifying monomer was replaced with pentaerythritol triacrylate (TMPTA) in an amount of 0.810 g (the molar ratio to the added allyl diglycol carbonate was 3:100).

[0094] Example 13

[0095] The modified allyl diglycol carbonate sheet was prepared in a manner similar to Example 1, except that the modifying monomer was replaced with polydipentaerythritol hexaacrylate (DPHA) in an amount of 1.582 g (the molar ratio to the added allyl diglycol carbonate was 3:100).

[0096] Example 14

[0097] Modified allyl diglycol carbonate was prepared in a manner similar to Example 1, except that the modifying monomer was replaced by a mixture of pentaerythritol triacrylate and polydipentaerythritol hexaacrylate, wherein the molar ratio of pentaerythritol triacrylate and polydipentaerythritol hexaacrylate was 1:1 (masses were 0.405 g and 0.791 g, respectively), and the molar ratio of the total added amount to allyl diglycol carbonate was 3:100. The initiator was replaced by a mixture of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, with a total added amount of 1.25 g, wherein the mass ratio of 2-hydroxy-2-methyl-1-phenyl-1-propanone to 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone was 2:1.

[0098] Example 15

[0099] Modified allyl diglycol carbonate was prepared in a manner similar to Example 1, except that the modified monomer was replaced by a mixture of 2,4,6-triallyloxy-1,3,5-triazine and polydipentaerythritol hexaacrylate, and the molar ratio of the total amount added to the allyl diglycol carbonate was 3:100, wherein the molar ratio of 2,4,6-triallyloxy-1,3,5-triazine and polydipentaerythritol hexaacrylate was 1:1 (masses were The initiator was replaced with a mixture of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, with a total addition amount of 1.25 g, wherein the mass ratio of 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone was 2:1.

[0100] Comparative Example

[0101] Comparative Example 1

[0102] Modified allyl diglycol carbonate was prepared in a manner similar to Example 1, except that tripropylene glycol diacrylate was not added.

[0103] Comparative Example 2

[0104] Polyallyl diglycol carbonate was prepared in a manner similar to Example 1, except that tripropylene glycol diacrylate was not added and 0.125 g of 3,6-dioxa-1,8-octanedithiol (DODT) was added.

[0105] Experimental example

[0106] Experimental Example 1 Conversion Rate Test

[0107] The monomer double bond conversion rate of Examples 1-13 and Comparative Examples 1-2 was tested by FTIR. The test results are as follows: Figure 1 and Figure 2 shown.

[0108] from Figure 1 and 2 It can be seen that the monomer conversion rates of Examples 1-13 are all above 88%, and there is no obvious decrease compared with Comparative Examples 1 and 2, indicating that the addition amount of the modified monomer has little effect on the conversion rate. The preparation method of the present invention can achieve a higher monomer conversion rate in a short time.

[0109] Experimental Example 2 Transmittance Test

[0110] The transmittance of the products obtained in Examples 1-8 was tested using a TU-1810 UV-visible spectrophotometer under the following conditions: air humidity less than 70% and a fast scanning speed. Figure 3 and Figure 4 shown.

[0111] Depend on Figure 3 and Figure 4 It can be seen that the transmittance of the products obtained in Examples 1-13 is all above 85%, which is not significantly lower than that in Comparative Examples 1 and 2, indicating that the allyl diglycol carbonate sheet obtained by the preparation method of the present invention has high transmittance.

[0112] Experimental Example 3 Yellow Index Test

[0113] The yellow index test was performed on the products obtained in Examples 1-13. The transmittance of the products at wavelengths of 450nm and 650nm was tested respectively. The test conditions were as follows: air humidity was less than 70%, single point detection was performed, and the yellow index was calculated by formula (1) and formula (2). The test results of Example 1, Example 3 and Example 6 are shown in Figure 2. Figure 3 shown.

[0114] Y=1-T 450 / T 650 Formula (1);

[0115] YI=96Y Formula (2);

[0116] Among them, T 450 and T 650 They are the transmittance at 450nm and 650nm respectively, and YI is the yellowness index.

[0117] The test results are as follows Figure 5 and Figure 6 As shown, YI is the yellowness index. When YI = 1.5, the resin is colorless; when YI = about 5, the resin is light yellow.

[0118] from Figure 5 It can be seen that the yellowness index of the products obtained in Examples 1-6 is relatively low, below 3.5. Figure 6 It can be seen that the yellowness index of the resins modified with different modifying monomers varies greatly, and is slightly higher than that of Comparative Examples 1 and 2, but is generally below 6, indicating that the yellowness index of the allyl diglycol carbonate sheet prepared by the present invention is low.

[0119] Experimental Example 4 Etching Track Test

[0120] Cut the entire track sheet into 3cm×5cm specifications with a laser, wash away the dust on the surface with deionized water, wipe dry the water, and place the track sheet parallel to the nuclide. 238 U+226 Ra+ 232 The sample was irradiated 1 cm above the mixed source of Th for 1 hour. After the sample was removed, the dust on the surface was washed off and etched with 6.25 mol / L NaOH solution for 6 hours at an etching temperature of 70°C. The sample was etched vertically in the etching solution.

[0121] The overall etch rate V was measured gravimetrically. b , using the following formula:

[0122] V b = Δm / (2Aρt) Formula (3)

[0123] In the above formula:

[0124] Δm—loss of polymer weight within etching time t;

[0125] A—sheet surface area;

[0126] ρ—density of the sheet;

[0127] t—etching time.

[0128] The body etch rate graphs of Examples 1-13 are as follows: Figure 7 and Figure 8 .from Figure 7 It can be analyzed that the volume etching rate of modified resins with different BPA-DA addition amounts is different, and the smallest one is when 3% is added. Figure 8 It can be seen that the etching rates of the resin bodies modified with different monomers are different.

[0129] Track efficiency calculation formula:

[0130] ε=N j / A Formula (4)

[0131] Nj—net track density measured by the material standard source;

[0132] A—Surface emissivity of a standard plane source.

[0133] Among them, the standard radioactive source used is nuclide 238 U+ 226 Ra+ 232 Mixed source of Th, α radioactivity specific activity 168±1.2α decays / cm 2 The etched track slices were observed under an optical microscope and photographed.

[0134] Figure 9 and Figure 10 The track detection efficiency of Examples 1-13 and Comparative Examples 1 and 2 is shown. Compared with Comparative Examples 1 and 2, it can be seen that the track detection effect is enhanced after adding the modified monomer.

[0135] Figure 12 Microscope images of the resins prepared in Examples 1-13 and Comparative Examples 1 and 2 after track etching. The results show that the resins prepared in Examples 1-13, when fabricated into track detectors, can effectively detect alpha ray tracks. Compared to Comparative Examples 1 and 2, the displayed tracks are clearer and the background noise is reduced.

[0136] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A modified allyl diglycol carbonate sheet for track detection, characterized in that: The modified allyl diglycol carbonate sheet is prepared by curing allyl diglycol carbonate and a modified monomer under ultraviolet light.

2. The modified allyl diglycol carbonate sheet according to claim 1, characterized in that: The modified monomer is selected from one or more of the following (meth) acrylate monomers: triethylene glycol dimethacrylate (TEDMA), diethylene glycol dimethacrylate (DEGMA), diallyl phthalate (DAP), diallyl terephthalate (DATP), neopentyl glycol diacrylate (NPGDA), ethylene glycol dimethacrylate (EGDMA), tripropylene glycol diacrylate (BPA-DA), ethoxylated trimethylolpropane triacrylate (ETPTA), tripropylene glycol trimellitate (TRPTA), and dipropylene glycol diacrylate (DATP). The following are some of the following compounds: AIM-705), trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), trimethylolpropane trimethacrylate (TMPTMA), glycerol trihydroxypropyl ether triacrylate (GPTA), ditrimethylolpropane tetraacrylate (DI-TMPAT), pentaerythritol tetraacrylate (PET4A), polydipentaerythritol pentaacrylate (PTMPT), polydipentaerythritol hexaacrylate (DPHA) and 2,4,6-triallyloxy-1,3,5-triazine (TAC).

3. The allyl diglycol carbonate sheet according to claim 1, characterized in that: The molar ratio of the modified monomer to allyl diglycol carbonate is (0.001-0.2):

1.

4. The allyl diglycol carbonate sheet according to claim 1, characterized in that: Allyl diglycol carbonate and modified monomers are cured under ultraviolet light initiator, and the ultraviolet light initiator is selected from one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone (i.e., 1173), benzoin dimethyl ether, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone and 2,4,6-trimethylbenzoyldiphenoxyphosphine.

5. The allyl diglycol carbonate sheet according to claim 4, characterized in that: The mass ratio of the ultraviolet light initiator to allyl diglycol carbonate is (0.01-0.2):

1.

6. A method for preparing a modified allyl diglycol carbonate sheet for track detection, characterized in that: The method comprises the following steps: Step 1: Mix raw materials including allyl diglycol carbonate, modified monomer and ultraviolet initiator and place them in a mold; Step 2: Place the mold under an ultraviolet light source for curing to obtain a modified allyl diglycol carbonate sheet.

7. The method according to claim 6, characterized in that In step 2, The curing temperature is 20-30°C.

8. The method according to claim 6, characterized in that In step 2, The curing time is 10 to 60 minutes.

9. The method according to claim 6, characterized in that In step 2, The power of the ultraviolet light source is 20 to 100W; The distance between the mold and the ultraviolet light source is 5 to 30 cm.

10. Use of the modified allyl diglycol carbonate sheet according to any one of claims 1 to 5 or the modified allyl diglycol carbonate sheet prepared by the preparation method according to any one of claims 6 to 9 for solid nuclear track detection.

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