CN116474157B - Preparation method and system of hard tissue biological adhesive for continuous adhesion in wet environment - Google Patents

Preparation method and system of hard tissue biological adhesive for continuous adhesion in wet environment Download PDF

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CN116474157B
CN116474157B CN202310476200.3A CN202310476200A CN116474157B CN 116474157 B CN116474157 B CN 116474157B CN 202310476200 A CN202310476200 A CN 202310476200A CN 116474157 B CN116474157 B CN 116474157B
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reaction
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offset
moment
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CN116474157A (en
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施雪涛
吴凯
宣承楷
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Guangzhou Xunhe Medical Technology Co ltd
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    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06T—IMAGE DATA PROCESSING OR GENERATION, IN GENERAL
    • G06T7/00—Image analysis
    • G06T7/0002—Inspection of images, e.g. flaw detection
    • G06T7/0004—Industrial image inspection
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06T—IMAGE DATA PROCESSING OR GENERATION, IN GENERAL
    • G06T1/00—General purpose image data processing
    • G06T1/0014—Image feed-back for automatic industrial control, e.g. robot with camera
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06T—IMAGE DATA PROCESSING OR GENERATION, IN GENERAL
    • G06T7/00—Image analysis
    • G06T7/10—Segmentation; Edge detection
    • G06T7/12—Edge-based segmentation
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06T—IMAGE DATA PROCESSING OR GENERATION, IN GENERAL
    • G06T7/00—Image analysis
    • G06T7/10—Segmentation; Edge detection
    • G06T7/13—Edge detection
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06T—IMAGE DATA PROCESSING OR GENERATION, IN GENERAL
    • G06T2207/00—Indexing scheme for image analysis or image enhancement
    • G06T2207/30—Subject of image; Context of image processing
    • G06T2207/30108—Industrial image inspection
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The application belongs to the technical field of biomedical glue and intelligent manufacturing, and provides a preparation method and a system of a hard tissue biological adhesive for continuously bonding in a wet environment, which specifically comprise the following steps: in the preparation process of the aromatic polyurethane prepolymer, a viscosity measurement value is obtained by arranging a viscometer in a reaction container, an industrial digital camera is arranged, and a container image is obtained by shooting with the industrial digital camera; and calculating a miscellaneous offset sequence through the container image, calculating the mediation expansion degree according to the viscosity measurement value and the miscellaneous offset sequence of the reaction container, and finally controlling the reaction process by combining the mediation expansion degree. By using the characteristic of the side reaction caused by impurities, the side reaction of the reaction can be observed through color change, so that the degree of obstruction of the reaction progress can be quantified, and the accuracy of the end point of the prediction process is improved; and the synchronous monitoring of a plurality of reaction containers optimizes the time of synchronous mediation, greatly reduces the waste of productivity and improves the production efficiency.

Description

Preparation method and system of hard tissue biological adhesive for continuous adhesion in wet environment
Technical Field
The application belongs to the technical fields of biomedical glue and intelligent manufacturing, and particularly relates to a preparation method and a system of a hard tissue biological adhesive for continuous adhesion in a wet environment.
Background
In the synthetic process for preparing the hard polyether polyurethane adhesive, the main reaction is the process that-NCO is consumed by-OH in practice, so that the reaction end point is positively related to the-NCO concentration in the system, and can be judged by a di-n-butylamine titration method, while the moisture in the air consumes-NCO, and meanwhile, the oxygen in the air also consumes-CNO, the problem that the vacuum degree is insufficient, nitrogen leaks and the like are difficult to overcome is easily existed in the practical operation process, the problems easily cause the huge difference of the termination time of the same reaction process, quite unfavorable unstable factors are brought to the large-scale preparation of the medical adhesive, the immeasurable chemical raw materials are wasted due to the incomplete reaction process, the production energy is wasted due to the empty time after the reaction is completed, and the immeasurable economic loss is brought to the large-scale production. Therefore, if the termination time point of the process cannot be dynamically reacted, the mass production of the medical adhesive will not achieve the desired productivity. In the synthetic reaction process, the viscosity can reflect the progress of the reaction process to a certain extent, but as the generation speed or the reaction rate of the product continuously changes along with the progress, the problem of impurities always exists, so that the ending end point of the progress cannot be accurately predicted; the side reaction of the reaction can observe the side reaction caused by impurities through color change, thereby providing the obstructive quantification of the reaction progress and improving the accuracy of the ending end point of the prediction process; the yield or purity can also be improved in medical adhesives, and the risks of cytotoxicity and tissue rejection caused by residual unreacted monomers can be reduced.
Disclosure of Invention
The application aims to provide a preparation method and a preparation system of a hard tissue biological adhesive for continuous adhesion in a wet environment, which are used for solving one or more technical problems in the prior art and at least providing a beneficial selection or creation condition.
In order to achieve the above object, according to an aspect of the present application, there is provided a method for preparing a hard tissue bioadhesive for continuous adhesion in a wet environment, the hard tissue bioadhesive comprising a component a and a component B, wherein the component a is an aromatic polyurethane prepolymer based on short-chain polyethylene glycol and small-molecule polyol, the component B is an aromatic modified secondary amine curing agent, and the component a and the component B are mixed according to a ratio of functional group molar amounts (-NCO: -NH) =1:1 to form the hard tissue bioadhesive.
Further, the method for obtaining the component A comprises the following steps: reacting short-chain polyethylene glycol (short-chain PEG) with diphenylmethane diisocyanate (MDI) to obtain an intermediate, and adding a micromolecular polyol chain extender to obtain an aromatic polyurethane prepolymer; the ratio of the molar amount of-NCO functional groups of LDI to the molar amount of-OH functional groups of PEG in the intermediate ranges from 2:1 to 3:1; the ratio of the molar amount of-NCO functional groups of LDI to the molar amount of-OH functional groups of PEG in the aromatic polyurethane prepolymer ranges from 1.8:1 to 2:1; the short-chain PEG consists of one or more of PEG200, PEG400 and PEG 600; the micromolecular polyol chain extender consists of one or more of glycerol, pentaerythritol and glucose;
the method for obtaining the component B comprises the following steps: combining an aromatic diprimary amine with an alpha, beta-unsaturated carbonyl compound according to a functional group molar ratio-NH 2: -c=c is 1.2:1, reacted under transition metal catalysis conditions of 0.1% mass fraction, followed by separation by column chromatography to obtain the aromatic modified secondary amine curing agent.
Further, the process for obtaining the aromatic polyurethane prepolymer comprises the following steps:
s100, arranging a viscometer in a reaction container, and obtaining a viscosity measurement value through the viscometer;
s200, arranging an industrial digital camera, and shooting by using the industrial digital camera to obtain a container image;
s300, calculating a miscellaneous offset sequence through the container image;
s400, calculating the mediation expansion degree according to the viscosity measurement value and the impurity offset sequence of the reaction container;
s500, controlling the reaction process by combining the mediated expansion degree.
Further, in step S100, a viscometer is disposed in the reaction vessel, and a method of obtaining a viscosity measurement value by the viscometer is: the viscometer is any one of a Brookfield viscometer, a vibrating online viscometer or a rotary viscometer; the viscosity of the liquid in the reaction vessel is measured by a viscometer in real time to obtain a viscosity measurement value, wherein the time interval for obtaining the viscosity measurement value is T, and the value range of T is between 0.5s and 2 s.
Further, in step S200, an industrial digital camera is arranged and used to capture images of the container by the industrial digital camera, which may be an industrial CCD camera or a cmos camera; shooting the solution in the reaction container by an industrial digital camera, carrying out graying treatment on the obtained image, identifying and intercepting the area of the solution in the reaction container in the image by an edge detection algorithm, and finally intercepting the obtained image to be used as a container image; wherein the frequency of acquiring the container image is the same as the time interval for acquiring the viscosity measurement.
Further, in step S300, the method of calculating the miscellaneous offset sequence from the container image is:
the gray values of all pixels in the container image are arranged in order from small to large to form a first gray sequence, and a fragment from the upper quartile to the lower quartile of the first gray sequence is intercepted to be used as a second gray sequence;
the average value of each element of the second gray level sequence is recorded as egr_ sls, and the sub dip parameter value sd_idx is calculated and obtained: sd_idx=ceil (60/T); (where T is the time interval for taking viscosity measurements and ceil () is an upward rounding function;)
The egr_ sls obtained at each time is used to form a sequence called an average ash sequence egr_ls, the i1 represents the sequence number of the time, and egr_ls i1 Represents the i1 element of the gray sequence; calculating the offset parameter ly_idx at the i1 st moment i1 :
ly_idx i1 ＝min{egr_ls[(i1－sd_idx):i1]}exp(egr_ls i1 ÷egr_ls i1-1 )；
Wherein min { } is a minimum function, egr_ls [ (i 1-sd_idx): i1] represents the set of the i1-sd_idx to i1 elements of the gray-balancing sequence;
taking a sequence formed by offset parameter values at each moment as an offset sequence, if one element in the offset sequence is larger than the previous element, defining that the moment corresponding to the element meets an offset condition, acquiring each offset moment and forming a sequence as a impurity-related offset sequence;
the problem of insufficient data concentration in the process of screening and obtaining the impurity-related offset sequence is that the data screening condition is thin and direct in the process of obtaining the result, and the phenomenon of periodical high-drift of gray values in images cannot be accurately positioned, however, the problem cannot be solved in the prior art, and in order to make the impurity-related offset sequence more consistent with the screening condition and solve the problem, and eliminate the phenomenon of thin data screening condition, the application proposes a more preferable scheme as follows:
preferably, in step S300, the method of calculating the miscellaneous offset sequence by the container image may further be: the gray values of all pixels in the container image are arranged in order from small to large to form a first gray sequence, and a fragment from the upper quartile to the lower quartile of the first gray sequence is intercepted to be used as a second gray sequence;
the arithmetic average value of each element of the second gray level sequence is denoted as egr_ sls, and the median value of the second gray level sequence is denoted as mgr_ sls; noi _ sls represents the number of elements in the second gray level sequence; calculating to obtain a basic gray sign value bs_grsv:
wherein exp () represents an exponential function with the natural constant e as a base;
the difference value between mgr_ sls of one moment and the last moment is called as a middle gray difference m_dis, and the middle gray differences of all the moments in history are acquired to form a sequence which is called as a first gray difference sequence; if the values of a plurality of continuous elements in the first gray difference sequence are all larger than 0 or are all smaller than 0, defining that a unidirectional stepping event occurs at the plurality of moments, and taking the moment number of the plurality of moments as the unidirectional stepping length of the unidirectional stepping event; searching to obtain each unidirectional stepping event in the first gray difference sequence, and taking the arithmetic average value of the unidirectional stepping length of each unidirectional stepping event as an auxiliary sinking parameter value fd_idx;
calculating a dip parameter sk_gap: sk_gap=min fd_idx, ceil (60/T) +;
where T is the time interval in which the viscosity measurement is taken and ceil () is an upward rounding function; taking the minimum value in the front sk_gap gray scale values at the current moment as a quasi gray scale value; constructing a sequence of quasi gray scale values at each time in history as quasi gray scale sequence; if one element in the quasi gray sequence is larger than the value of the previous element, marking the moment as a first offset moment; and obtaining each first offset moment to form a sequence as a miscellaneous offset sequence.
The beneficial effects are that: the impurity-related offset sequence is obtained by calculation according to the gray level change characteristics in the container image, so that the time position of gray level aggravating change can be accurately marked, preparation is made for quantifying the viscosity change trend or quantifying the reaction blocking degree by the position of gray level aggravating change, the characteristic information extraction on the change of viscosity along with the reaction progress in the synthesis reaction process can be improved, and the accuracy is improved for further regulating the reaction end point.
Further, in step S400, according to the viscosity measurement value and the impurity offset sequence of the reaction vessel, the method for calculating the mediated expansion degree is as follows:
the difference between a viscosity measurement at a moment and the previous moment is represented by the viscosity residual at that moment; taking the time in the impurity offset sequence as the impurity time; obtaining viscosity residual errors at all times in the history of the reaction container to construct a sequence as a residual error sequence;
if the value of one element in the residual sequence is larger or smaller than the values of the previous element and the next element, defining the moment corresponding to the element as an auxiliary mark moment;
the time which is the auxiliary mark time and the impurity time in the residual sequence is recorded as a first mark point; the number of first mark points in the residual sequence is nomls; the mediated expansion degree ct_idx of the reaction vessel is calculated as follows:
wherein i3 is used as the serial number of the first mark point, and the section from i3 to i3-1 first mark points in the residual sequence is intercepted and marked as mls i3 The method comprises the steps of carrying out a first treatment on the surface of the In mls i3 (l) Represents mls i3 The last element in (a); e_mls i3 Represents mls i3 Each element of (a)Is the average value of (2); ds_mls i3 Is mls i3 The difference between the maximum and minimum of the elements.
Since the phenomenon of marking deviation often occurs in the process of calculating the mediated expansion degree, which can lead to the problem of data alignment at the marking moment and the impurity moment, the prior art cannot solve the problem of data alignment, and in order to make the problem better and solve, and eliminate the phenomenon of marking deviation, the application provides a more preferable scheme as follows:
preferably, in step S400, the method for calculating the mediated expansion degree according to the viscosity measurement value and the miscellaneous offset sequence of the reaction vessel may further be:
the difference between a viscosity measurement at a moment and the previous moment is represented by the viscosity residual at that moment; taking the time in the impurity offset sequence as the impurity time; obtaining viscosity residual errors at all times in the history of the reaction container to construct a sequence as a residual error sequence;
in each impurity-related time, if the impurity-related time is a continuous time, defining that a progress suppression event occurs at the continuous time; the number of the moments occupied by the progress suppression events is recorded as a suppression distance hdds, and the median of the suppression distances of the progress suppression events is obtained as a suppression distance reference;
if the suppression distance of the progress suppression event is greater than or equal to the suppression distance reference, the first impurity time and the last impurity time of the progress suppression event are used as suppression mark point time; if the inhibition distance of the progress inhibition event is greater than or equal to the inhibition distance reference, taking the time of the position in the middle of the progress inhibition event as the inhibition mark point time; if two positions in the progress suppression event are at the middle time, selecting the time closest to the other suppression event as the suppression mark point time; (wherein the time closest to another suppression event refers to selecting the former if one of the suppression events closest to the current suppression event occurs before the current suppression event, and selecting the latter otherwise);
calculating a break adaptation value LssRt at each mark point moment:
intercepting a sequence from the moment of a current mark point to the moment of a previous mark point in the intercepted residual sequence and recording the sequence as stls;
LssRt＝ln(|mean(larger)/mean(stls)|)；
where mean () is an average function, and larger is each value in stls whose value is greater than mean (larger); the mediated expansion degree ct_idx of the reaction vessel is calculated as follows:
wherein i2 is an accumulated variable, nols is the number of marker point moments, lssRt i2 Represents the break adaptation value, rsk, at the i2 nd marker point instant i2 For the suppression probability, the representative value is the ratio of the total amount of the mark point time from the i 2-th mark point time to the current time to the total amount of the impurity-related time.
The beneficial effects are that: in the reaction process, the viscosity can reflect the progress of the reaction process to a certain extent, but as the generation speed or the reaction rate of the product continuously changes along with the process, the problems of insufficient impurity or air degree, nitrogen leakage and the like exist, and the ending end point of the process cannot be accurately predicted; the side reaction of the reaction can observe the side reaction caused by impurities through color change, and the combination of the side reaction and the impurity can provide the obstructive quantification of the reaction progress, thereby improving the accuracy of predicting the ending end point of the progress.
Further, in step S500, the method for controlling the reaction process in combination with mediating the expansion degree is as follows: the default reaction time of the reactants in the reaction vessel was designated prd;
acquiring the mediated expansion degree of each reaction container to form an expansion sequence;
the average value of the maximum value and the minimum value in the extended sequence is denoted as sepi, and the average value of the extended sequence is denoted as eoi; overall mediated expansion coefficient set_rg: set_rg= eoi/sepi; the total mediation time is set_len: set_len= prd ×set_rg;
after the duration from the reaction to prd/2, starting to record each total mediation time set_len and constructing a sequence as a mediation parameter sequence; the minimum value in the mediation parameter value sequence is the optimal mediation time; and continuously obtaining the optimal reaction time, and stopping the reaction progress of the reaction vessel when the reaction time reaches the optimal mediation time.
Further, the aromatic diprimary amine is composed of one or more of p-xylylenediamine, p-phenylenediamine, 4' -bis (4-aminophenoxy) biphenyl and biphenyl dimethylamine; the alpha, beta-unsaturated carbonyl compound consists of one or more of methyl acrylate, butyl acrylate and diethyl maleate; the transition metal consists of one or more of ceric ammonium nitrate, yttrium nitrate, cobalt chloride and ferric chloride.
Preferably, all undefined variables in the present application, if not explicitly defined, may be thresholds set manually.
The application also provides a preparation system of the hard tissue biological adhesive continuously bonded in a wet environment, which comprises the following steps: a processor, a memory, and a computer program stored in the memory and executable on the processor, wherein the processor implements the steps in the method for preparing a wet environment continuous bonding hard tissue biological adhesive when the computer program is executed, the preparation system of the wet environment continuous bonding hard tissue biological adhesive can be executed in a computing device such as a desktop computer, a notebook computer, a palm computer, a cloud data center, and the like, and the executable system can comprise, but is not limited to, a processor, a memory, and a server cluster, and the processor executes the computer program to be executed in a unit of the following system:
a viscosity acquisition unit for arranging a viscometer in the reaction vessel and obtaining a viscosity measurement value by the viscometer;
an image photographing unit for arranging an industrial digital camera and photographing with the industrial digital camera to obtain a container image;
the impurity quantization unit is used for calculating an impurity offset sequence through the container image;
the mediation model unit is used for calculating mediation expansion degree according to the viscosity measurement value and the impurity offset sequence of the reaction container;
and the dynamic adjusting unit is used for controlling the reaction process by combining the mediated expansion degree.
The beneficial effects of the application are as follows: the application provides a preparation method and a system of a hard tissue biological adhesive for continuous adhesion in a wet environment, which can observe the characteristics of side reactions caused by impurities through color change by utilizing the side reactions of the reactions, thereby providing the obstructive quantification of the reaction progress and improving the accuracy of the ending end point of a prediction process; because each reaction container is required to be synchronously operated in the same batch production process, the operation smoothness and the production efficiency of a preparation assembly line are improved, synchronous monitoring of a plurality of reaction containers is beneficial to optimizing the time of synchronous mediation, the waste of productivity is greatly reduced, and the production efficiency is improved.
Drawings
The above and other features of the present application will become more apparent from the detailed description of the embodiments thereof given in conjunction with the accompanying drawings, in which like reference characters designate like or similar elements, and it is apparent that the drawings in the following description are merely some examples of the present application, and other drawings may be obtained from these drawings without inventive effort to those of ordinary skill in the art, in which:
FIG. 1 is a flow chart of a method of preparing a hard tissue bioadhesive for continuous bonding in a wet environment;
FIG. 2 is a block diagram of a system for preparing a hard tissue bio-adhesive for continuous adhesion in a wet environment.
Detailed Description
The conception, specific structure, and technical effects produced by the present application will be clearly and completely described below with reference to the embodiments and the drawings to fully understand the objects, aspects, and effects of the present application. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Referring to fig. 1, which is a flowchart illustrating a method for preparing a wet environment-continuously bonded hard tissue bio-adhesive, a method for preparing a wet environment-continuously bonded hard tissue bio-adhesive according to an embodiment of the present application will be described with reference to fig. 1, the method comprising the steps of:
example 1: the hard tissue biological adhesive comprises a component A and a component B, wherein the component A is an aromatic polyurethane prepolymer based on short-chain polyethylene glycol and small-molecule polyol, the component B is an aromatic modified secondary amine curing agent, and the component A and the component B are mixed according to the molar ratio of functional groups (-NCO: -NH) =1:1 to form the hard tissue biological adhesive.
Further, the method for obtaining the component A comprises the following steps: reacting short-chain polyethylene glycol (short-chain PEG) with diphenylmethane diisocyanate (MDI) to obtain an intermediate, and adding a micromolecular polyol chain extender to obtain an aromatic polyurethane prepolymer; the ratio of the molar amount of-NCO functional groups of LDI to the molar amount of-OH functional groups of PEG in the intermediate is 2:1; the ratio of the molar amount of-NCO functional groups of LDI to the molar amount of-OH functional groups of PEG in the aromatic polyurethane prepolymer is 1.9:1; the short-chain PEG is a mixture of PEG200 and PEG400 with equimolar quantity; the small molecule polyalcohol chain extender is glycerol;
the method for obtaining the component B comprises the following steps: combining an aromatic diprimary amine with an alpha, beta-unsaturated carbonyl compound according to a functional group molar ratio-NH 2: -c=c is 1.2:1, reacted under transition metal catalysis conditions of 0.1% mass fraction, followed by separation by column chromatography to obtain the aromatic modified secondary amine curing agent.
Further, the process for obtaining the aromatic polyurethane prepolymer comprises the following steps:
s100, arranging a viscometer in a reaction container, and obtaining a viscosity measurement value through the viscometer;
s200, arranging an industrial digital camera, and shooting by using the industrial digital camera to obtain a container image;
s300, calculating a miscellaneous offset sequence through the container image;
s400, calculating the mediation expansion degree according to the viscosity measurement value and the impurity offset sequence of the reaction container;
s500, controlling the reaction process by combining the mediated expansion degree.
Further, in step S100, a viscometer is disposed in the reaction vessel, and a method of obtaining a viscosity measurement value by the viscometer is: the viscometer is a vibrating online viscometer; the viscosity measurement was performed on the liquid in the reaction vessel by a viscometer in real time to measure the obtained value as a viscosity measurement value, wherein the time interval for obtaining the viscosity measurement value was T, t=1 s.
Further, in step S200, an industrial digital camera is arranged and used to capture images of the container by the industrial digital camera, which may be an industrial CCD camera; shooting the solution in the reaction container by an industrial digital camera, carrying out graying treatment on the obtained image, identifying and intercepting the area of the solution in the reaction container in the image by an edge detection algorithm, and finally intercepting the obtained image to be used as a container image; wherein the frequency of acquiring the container image is the same as the time interval for acquiring the viscosity measurement.
Further, in step S300, the method of calculating the miscellaneous offset sequence from the container image is:
the gray values of all pixels in the container image are arranged in order from small to large to form a first gray sequence, and a fragment from the upper quartile to the lower quartile of the first gray sequence is intercepted to be used as a second gray sequence;
the average value of each element of the second gray level sequence is recorded as egr_ sls, and the sub dip parameter value sd_idx is calculated and obtained: sd_idx=ceil (60/T);
the egr_ sls obtained at each time is used to form a sequence called an average ash sequence egr_ls, the i1 represents the sequence number of the time, and egr_ls i1 Represents the i1 element of the gray sequence; calculating the offset parameter ly_idx at the i1 st moment i1 :
ly_idx i1 ＝min{egr_ls[(i1－sd_idx):i1]}exp(egr_ls i1 ÷egr_ls i1-1 )；
Wherein min { } is a minimum function, egr_ls [ (i 1-sd_idx): i1] represents the set of the i1-sd_idx to i1 elements of the gray-balancing sequence;
taking a sequence formed by offset parameter values at each moment as an offset sequence, if one element in the offset sequence is larger than the previous element, defining that the moment corresponding to the element meets an offset condition, acquiring each offset moment and forming a sequence as a impurity-related offset sequence;
further, in step S400, according to the viscosity measurement value and the impurity offset sequence of the reaction vessel, the method for calculating the mediated expansion degree is as follows:
the difference between a viscosity measurement at a moment and the previous moment is represented by the viscosity residual at that moment; taking the time in the impurity offset sequence as the impurity time; obtaining viscosity residual errors at all times in the history of the reaction container to construct a sequence as a residual error sequence;
if the value of one element in the residual sequence is larger or smaller than the values of the previous element and the next element, defining the moment corresponding to the element as an auxiliary mark moment;
the time which is the auxiliary mark time and the impurity time in the residual sequence is recorded as a first mark point; the number of first mark points in the residual sequence is nomls; the mediated expansion degree ct_idx of the reaction vessel is calculated as follows:
wherein i3 is used as the serial number of the first mark point, and the section from i3 to i3-1 first mark points in the residual sequence is intercepted and marked as mls i3 The method comprises the steps of carrying out a first treatment on the surface of the In mls i3 (l) Represents mls i3 The last element in (a); e_mls i3 Represents mls i3 The average value of each element in the list; ds_mls i3 Is mls i3 The difference between the maximum and minimum of the elements.
Further, in step S500, the method for controlling the reaction process in combination with mediating the expansion degree is as follows: the default reaction time of the reactants in the reaction vessel was designated prd;
acquiring the mediated expansion degree of each reaction container to form an expansion sequence;
the average value of the maximum value and the minimum value in the extended sequence is denoted as sepi, and the average value of the extended sequence is denoted as eoi; overall mediated expansion coefficient set_rg: set_rg= eoi/sepi; the total mediation time is set_len: set_len= prd ×set_rg;
after the duration from the reaction to prd/2, starting to record each total mediation time set_len and constructing a sequence as a mediation parameter sequence; the minimum value in the mediation parameter value sequence is the optimal mediation time; and continuously obtaining the optimal reaction time, and stopping the reaction progress of the reaction vessel when the reaction time reaches the optimal mediation time.
Further, the aromatic diprimary amine is p-xylylenediamine; the alpha, beta-unsaturated carbonyl compound is diethyl maleate; the transition metal is yttrium nitrate.
Example 2:
the aromatic polyurethane prepolymer was prepared by the method in example 1, and example 2 differs from example 1 in that the method of calculating the miscellaneous offset sequence from the container image was:
the gray values of all pixels in the container image are arranged in order from small to large to form a first gray sequence, and a fragment from the upper quartile to the lower quartile of the first gray sequence is intercepted to be used as a second gray sequence;
the arithmetic average value of each element of the second gray level sequence is denoted as egr_ sls, and the median value of the second gray level sequence is denoted as mgr_ sls; noi _ sls represents the number of elements in the second gray level sequence; calculating to obtain a basic gray sign value bs_grsv:
wherein exp () represents an exponential function with the natural constant e as a base;
the difference value between mgr_ sls of one moment and the last moment is called as a middle gray difference m_dis, and the middle gray differences of all the moments in history are acquired to form a sequence which is called as a first gray difference sequence; if the values of a plurality of continuous elements in the first gray difference sequence are all larger than 0 or are all smaller than 0, defining that a unidirectional stepping event occurs at the plurality of moments, and taking the moment number of the plurality of moments as the unidirectional stepping length of the unidirectional stepping event; searching to obtain each unidirectional stepping event in the first gray difference sequence, and taking the arithmetic average value of the unidirectional stepping length of each unidirectional stepping event as an auxiliary sinking parameter value fd_idx;
calculating a dip parameter sk_gap: sk_gap=min fd_idx, ceil (60/T) +;
where T is the time interval in which the viscosity measurement is taken and ceil () is an upward rounding function; taking the minimum value in the front sk_gap gray scale values at the current moment as a quasi gray scale value; constructing a sequence of quasi gray scale values at each time in history as quasi gray scale sequence; if one element in the quasi gray sequence is larger than the value of the previous element, marking the moment as a first offset moment; and obtaining each first offset moment to form a sequence as a miscellaneous offset sequence.
Embodiment 2 also differs from embodiment 1 in that the method of calculating the mediated expansion degree is:
the difference between a viscosity measurement at a moment and the previous moment is represented by the viscosity residual at that moment; taking the time in the impurity offset sequence as the impurity time; obtaining viscosity residual errors at all times in the history of the reaction container to construct a sequence as a residual error sequence;
in each impurity-related time, if the impurity-related time is a continuous time, defining that a progress suppression event occurs at the continuous time; the number of the moments occupied by the progress suppression events is recorded as a suppression distance hdds, and the median of the suppression distances of the progress suppression events is obtained as a suppression distance reference;
if the suppression distance of the progress suppression event is greater than or equal to the suppression distance reference, the first impurity time and the last impurity time of the progress suppression event are used as suppression mark point time; if the inhibition distance of the progress inhibition event is greater than or equal to the inhibition distance reference, taking the time of the position in the middle of the progress inhibition event as the inhibition mark point time; if two positions in the progress suppression event are at the middle time, selecting the time closest to the other suppression event as the suppression mark point time; (wherein the time closest to another suppression event refers to selecting the former if one of the suppression events closest to the current suppression event occurs before the current suppression event, and selecting the latter otherwise);
calculating a break adaptation value LssRt at each mark point moment:
intercepting a sequence from the moment of a current mark point to the moment of a previous mark point in the intercepted residual sequence and recording the sequence as stls;
LssRt＝ln(|mean(larger)/mean(stls)|)；
where mean () is an average function, and larger is each value in stls whose value is greater than mean (larger); the mediated expansion degree ct_idx of the reaction vessel is calculated as follows:
wherein i2 is an accumulated variable, nols is the number of marker point moments, lssRt i2 Represents the break adaptation value, rsk, at the i2 nd marker point instant i2 For the suppression probability, the representative value is the ratio of the total amount of the mark point time from the i 2-th mark point time to the current time to the total amount of the impurity-related time.
Comparative example 1:
the aromatic polyurethane prepolymer was produced by the method of example 1, and comparative example 1 differs from example 1 in that the mediation time in the production of the aromatic polyurethane prepolymer was judged to be a conventional-NCO group detection method, and the specific method is as follows:
judging the mediation time of preparing the aromatic polyurethane prepolymer by a-NCO group (end point criterion) detection method:
C_Step1, preparing 0.1mol/L di-n-butylamine/toluene solution, 0.1mol/L hydrochloric acid aqueous solution (standard solution) and 1% mass fraction bromophenol blue/ethanol indicator;
C-Step2-0.1 g of prepolymer sample was weighed and placed in a 250ml conical flask (blank group without sample), 25ml of di-n-butylamine/toluene solution was added and stirred for 15 minutes to allow complete reaction;
adding 50ml of isopropanol and 3-4 drops of bromophenol blue indicator, then slowly dripping hydrochloric acid standard solution by using an acid burette, stopping after the color of the solution is changed from deep blue to yellow-green and kept for 1 minute without color change, and recording the volume of the hydrochloric acid standard solution to be consumed;
the calculation method of the-NCO concentration (mol/l) is as follows: nco= (V0-V) C/m; wherein V0 is the volume of the hydrochloric acid standard solution consumed by the blank group, V is the volume of the hydrochloric acid standard solution consumed by the experimental group, C is the concentration of the hydrochloric acid standard solution, and m is the mass of the prepolymer.
C_Step5-when the solution color in C_Step3 changes from bluish violet to yellowish green and the value of-NCO concentration (mol/l) reaches 50% of the initial value, the process for preparing the aromatic polyurethane prepolymer is mediated.
Table 1: comparative results of examples 1 to 2 and comparative example 1
Wherein, the test duration is the operation duration for judging the reaction end point of the process for preparing the aromatic polyurethane prepolymer in the comparative example; the test frequency is the number of times that the preparation process needs to carry out reaction termination judgment; the total time consumption of the test is the time length from the beginning to the end of the operation for judging the termination of the reaction; the complete preparation time is as follows: the duration of the process for preparing the aromatic polyurethane prepolymer (comprising checking the termination judgment of the reaction) from the beginning to the end; it can be seen from the table that the preparation methods of example 1 and example 2 have great advantages in terms of productivity, and the preparation efficiency of the examples is higher from the viewpoint of timeliness, and the results of the examples are more preferable from the viewpoint of the yield obtained by the preparation.
The system for preparing a hard tissue bio-adhesive with continuous bonding in a wet environment according to an embodiment of the present application is shown in fig. 2, which is a block diagram of the system for preparing a hard tissue bio-adhesive with continuous bonding in a wet environment according to the present application, and the system for preparing a hard tissue bio-adhesive with continuous bonding in a wet environment according to the embodiment includes: a processor, a memory, and a computer program stored in the memory and executable on the processor, which when executed, performs the steps of one embodiment of the preparation system for a wet environment continuous bonding hard tissue biological adhesive described above.
The system comprises: a memory, a processor, and a computer program stored in the memory and executable on the processor, the processor executing the computer program to run in units of the following system:
a viscosity acquisition unit for arranging a viscometer in the reaction vessel and obtaining a viscosity measurement value by the viscometer;
an image photographing unit for arranging an industrial digital camera and photographing with the industrial digital camera to obtain a container image;
the impurity quantization unit is used for calculating an impurity offset sequence through the container image;
the mediation model unit is used for calculating mediation expansion degree according to the viscosity measurement value and the impurity offset sequence of the reaction container;
and the dynamic adjusting unit is used for controlling the reaction process by combining the mediated expansion degree.
The preparation system of the hard tissue biological adhesive with the continuous adhesion in the wet environment can be operated in computing equipment such as a desktop computer, a notebook computer, a palm computer, a cloud server and the like. The preparation system of the hard tissue biological adhesive for continuous adhesion in a wet environment can comprise, but is not limited to, a processor and a memory. It will be appreciated by those skilled in the art that the examples are merely illustrative of one type of wet environment continuous bond hard tissue bio-adhesive preparation system and are not limiting of one type of wet environment continuous bond hard tissue bio-adhesive preparation system, and may include more or fewer components than examples, or may combine certain components, or different components, such as the one type of wet environment continuous bond hard tissue bio-adhesive preparation system may also include input and output devices, network access devices, buses, and the like.
The processor may be a central processing unit (Central Processing Unit, CPU), other general purpose processors, digital signal processors (Digital Signal Processor, DSP), application specific integrated circuits (Application Specific Integrated Circuit, ASIC), field programmable gate arrays (Field-Programmable Gate Array, FPGA) or other programmable logic devices, discrete gate or transistor logic devices, discrete hardware components, or the like. The general purpose processor may be a microprocessor or the processor may be any conventional processor or the like, which is a control center of the system for operating the preparation system for the wet environment continuous bonding hard tissue bio-adhesive, and which connects the various parts of the system for operating the preparation system for the whole wet environment continuous bonding hard tissue bio-adhesive by using various interfaces and lines.
The memory may be used to store the computer program and/or module, and the processor may implement various functions of the preparation system of the hard tissue bioadhesive for continuous bonding in a wet environment by running or executing the computer program and/or module stored in the memory and invoking data stored in the memory. The memory may mainly include a storage program area and a storage data area, wherein the storage program area may store an operating system, an application program (such as a sound playing function, an image playing function, etc.) required for at least one function, and the like; the storage data area may store data (such as audio data, phonebook, etc.) created according to the use of the handset, etc. In addition, the memory may include high-speed random access memory, and may also include non-volatile memory, such as a hard disk, memory, plug-in hard disk, smart Media Card (SMC), secure Digital (SD) Card, flash Card (Flash Card), at least one disk storage device, flash memory device, or other volatile solid-state storage device.
Although the present application has been described in considerable detail and with particularity with respect to several described embodiments, it is not intended to be limited to any such detail or embodiment or any particular embodiment so as to effectively cover the intended scope of the application. Furthermore, the foregoing description of the application has been presented in its embodiments contemplated by the inventors for the purpose of providing a useful description, and for the purposes of providing a non-essential modification of the application that may not be presently contemplated, may represent an equivalent modification of the application.

Claims (5)

1. A method for preparing a hard tissue bioadhesive which is continuously adhered in a wet environment, which is characterized in that the hard tissue bioadhesive comprises a component A and a component B, wherein the component A is an aromatic polyurethane prepolymer based on short-chain polyethylene glycol and small-molecule polyalcohol, the component B is an aromatic modified secondary amine curing agent, and the component A and the component B are NCO according to the molar ratio of functional groups: -nh=1:1 to form a hard tissue bioadhesive;
wherein the method for obtaining the component A comprises the following steps: reacting short-chain polyethylene glycol (short-chain PEG) with diphenylmethane diisocyanate (MDI) to obtain an intermediate, and adding a micromolecular polyol chain extender to obtain an aromatic polyurethane prepolymer; the ratio of the molar amount of-NCO functional groups of LDI to the molar amount of-OH functional groups of PEG in the intermediate ranges from 2:1 to 3:1; the ratio of the molar amount of-NCO functional groups of LDI to the molar amount of-OH functional groups of PEG in the aromatic polyurethane prepolymer ranges from 1.8:1 to 2:1; the short-chain PEG consists of one or more of PEG200, PEG400 and PEG 600; the micromolecular polyol chain extender consists of one or more of glycerol, pentaerythritol and glucose;
the method for obtaining the component B comprises the following steps: combining an aromatic diprimary amine with an alpha, beta-unsaturated carbonyl compound according to a functional group molar ratio-NH 2: -c=c 1.2:1, under transition metal catalysis conditions of 0.1% mass fraction, followed by separation by column chromatography to obtain an aromatic modified secondary amine curing agent;
wherein the process for obtaining the aromatic polyurethane prepolymer comprises the following steps:
s100, arranging a viscometer in a reaction container, and obtaining a viscosity measurement value through the viscometer;
s200, arranging an industrial digital camera, and shooting by using the industrial digital camera to obtain a container image;
s300, calculating a miscellaneous offset sequence through the container image;
s400, calculating the mediation expansion degree according to the viscosity measurement value and the impurity offset sequence of the reaction container;
s500, controlling the reaction process by combining the mediated expansion degree;
in step S300, the method for calculating the miscellaneous offset sequence from the container image is as follows: the gray values of all pixels in the container image are arranged in order from small to large to form a first gray sequence, and a fragment from the upper quartile to the lower quartile of the first gray sequence is intercepted to be used as a second gray sequence;
the average value of each element of the second gray level sequence is recorded as egr_ sls, and the sub dip parameter value sd_idx is calculated and obtained: sd_idx=ceil (60/T); the egr_ sls obtained at each time is used to form a sequence called an average ash sequence egr_ls, the i1 represents the sequence number of the time, and egr_ls i1 Represents the i1 element of the gray sequence; calculating the offset parameter ly_idx at the i1 st moment i1 :
ly_idx i1 ＝min{ egr_ls[(i1－sd_idx):i1]}exp(egr_ls i1 ÷egr_ls i1-1 )；
Wherein min { } is a minimum function, egr_ls [ (i 1-sd_idx): i1] represents the set of the i1-sd_idx to i1 elements of the gray-balancing sequence;
taking a sequence formed by offset parameter values at each moment as an offset sequence, if one element in the offset sequence is larger than the previous element, defining that the moment corresponding to the element meets an offset condition, acquiring each offset moment and forming a sequence as a impurity-related offset sequence;
in step S400, according to the viscosity measurement value and the impurity offset sequence of the reaction vessel, the method for calculating the mediated expansion degree is as follows: the difference between a viscosity measurement at a moment and the previous moment is represented by the viscosity residual at that moment; taking the time in the impurity offset sequence as the impurity time; obtaining viscosity residual errors at all times in the history of the reaction container to construct a sequence as a residual error sequence;
if the value of one element in the residual sequence is larger or smaller than the values of the previous element and the next element, defining the moment corresponding to the element as an auxiliary mark moment;
the time which is the auxiliary mark time and the impurity time in the residual sequence is recorded as a first mark point; the number of first mark points in the residual sequence is nomls; the mediated expansion degree ct_idx of the reaction vessel is calculated as follows:
；
wherein i3 is used as the serial number of the first mark point, and the section from i3 to i3-1 first mark points in the residual sequence is intercepted and marked as mls i3 The method comprises the steps of carrying out a first treatment on the surface of the In mls i3 (l) Represents mls i3 The last element in (a); e_mls i3 Represents mls i3 The average value of each element in the list; ds_mls i3 Is mls i3 Differences between maximum and minimum values in the elements;
in step S500, the method for controlling the reaction process in combination with the mediated expansion degree is as follows: the default reaction time of the reactants in the reaction vessel was designated prd;
acquiring the mediated expansion degree of each reaction container to form an expansion sequence; the average value of the maximum value and the minimum value in the extended sequence is denoted as sepi, and the average value of the extended sequence is denoted as eoi; overall mediated expansion coefficient set_rg: set_rg= eoi/sepi; the total mediation time is set_len: set_len= prd ×set_rg;
after the duration from the reaction to prd/2, starting to record each total mediation time set_len and constructing a sequence as a mediation parameter sequence; the minimum value in the mediation parameter value sequence is the optimal mediation time; and continuously obtaining the optimal reaction time, and stopping the reaction progress of the reaction vessel when the reaction time reaches the optimal mediation time.
2. The method for preparing a hard tissue bioadhesive for continuous adhesion in a wet environment according to claim 1, wherein in step S100, a viscometer is disposed in the reaction vessel and a viscosity measurement value is obtained by the viscometer by: the viscometer is any one of a Brookfield viscometer, a vibrating online viscometer or a rotary viscometer; and carrying out viscosity measurement on the liquid in the reaction container in real time by using a viscometer to obtain a viscosity measurement value, wherein the time interval for obtaining the viscosity measurement value is T, and the value range of T is 0.5 s-2 s.
3. The method for preparing a hard tissue bio-adhesive for continuous adhesion in a wet environment according to claim 1, wherein in step S200, an industrial digital camera is arranged and a container image is obtained by photographing with the industrial digital camera, wherein the industrial digital camera may be an industrial CCD camera or a cmos camera; shooting the solution in the reaction container by an industrial digital camera, carrying out graying treatment on the obtained image, identifying and intercepting the area of the solution in the reaction container in the image by an edge detection algorithm, and finally intercepting the obtained image to be used as a container image; wherein the frequency of acquiring the container image is the same as the time interval for acquiring the viscosity measurement.
4. The method for preparing a hard tissue bioadhesive for continuous adhesion in a wet environment according to claim 1, wherein said aromatic diprimary amine is composed of one or more of p-xylylenediamine, p-phenylenediamine, 4' -bis (4-aminophenoxy) biphenyl, biphenyl dimethylamine; the alpha, beta-unsaturated carbonyl compound consists of one or more of methyl acrylate, butyl acrylate and diethyl maleate; the transition metal consists of one or more of ceric ammonium nitrate, yttrium nitrate, cobalt chloride and ferric chloride.
5. A system for preparing a wet environment continuous bonding hard tissue bio-adhesive, the system comprising: a processor, a memory and a computer program stored in the memory and executable on the processor, the processor implementing the steps in a wet environment continuously bonded hard tissue bio-adhesive preparation method according to any one of claims 1 to 3 when the computer program is executed, the wet environment continuously bonded hard tissue bio-adhesive preparation system being run in a computing device of a desktop computer, a notebook computer, a palm computer and a cloud data center.
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